Fluid ionized compositions, methods of preparation and uses thereof

ABSTRACT

Disclosed herein are fluid ionized compositions, such as fluid calcium cyanamide fertilizer compositions, methods of preparation and uses thereof. In some examples, a fluid composition includes a mixture of about 40 to 20 parts of dissolved acid or acid-formed approximately neutral pH nitrogen plant nutrient compounds (such as urea ammonium nitrate and H 2 O) and about 1 to about 5 parts of a mixture of insoluble or weakly soluble high pH calcium-formed plant nutrient compounds (such as calcium cyanamide and H 2 O). The disclosed compositions and methods stabilize the compositions&#39; contained active nutrient ions and digested carbon. The disclosed compositions and methods facilitate controllable site-directed delivery of the contents of the compositions. The compositions and methods are effective for microbes nourishment plant fertilizing, soil amending, heavy metals leaching inhibition and, digesting organic proteinaceous excreta. The compositions are stable, easily calibrated, and non-clogging for soil injection, spray and irrigation water delivery to target sites.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.61/565,004, filed Nov. 30, 2011, which is incorporated herein byreference in its entirety.

FIELD

The present application relates to fertilizers and in particular, tofluid ionized compositions, such as fluid calcium cyanamide (CaNCN)fertilizer compositions, methods of preparation and uses thereof,including, without limitation, in industry and farming, plant feedingfertilizing, organism carbon feeding, nitrogen nutrient stabilization,alkaline phosphate nutrient stabilization, excreta digestionodor/organism inhibition, particle digestion, soil amending, synergisticalkaline tissue digestion, anti-corrosion and anti-freezing.

BACKGROUND

Today's energy costly to produce, nearly insoluble, granular, dry,carbon, calcium containing dry calcium cyanamide (CaNCN) nitrogenfertilizer that can stabilize nitrogen and phosphate with its carbon andcalcium. In moist to wet soil, as disclosed, its carbon feeds soilmicrobes, thus stabilizing its own nitrogen and compositions' containednitrogen from leaching and its calcium can inhibit phosphate losses intoenvironmental watersheds. It can also stabilize nitrogen and phosphatein other dry and fluid nitrogen fertilizers if combined with them. Ithas been used singly for fertilizing crops worldwide for more than ahundred years. However, dry calcium cyanamide fertilizer is associatedwith many disadvantages. For example, in addition to being energycostly, it has 50% lower nitrogen nutrient analysis than today's highnitrogen analysis, but leachable, urea. It requires up to twice as muchto be equivalently nutrient effective to feed plants nitrogen as ureadoes. Although dry CaNCN fertilizer has been shown to provide additionalancillary benefits to young and maturing plants' health, these benefitsare only observed when extremely large expensive quantities are used(such as application of hundreds of pounds per acre) making it far morecostly as compared to current plant protectants. Additionally,historically used large, but noxious dust free, calcium cyanamidegranules, to be fully hydrolyzed, must be in greater than 14× water(U.S. Pat. No. 7,785,388). This has been unreliable in sometimes poorly,rain-dependent, moistened soils for its macro and micro ionic nutrientsand ancillary benefits to be fully effective. Also, if its benefits areto aid other dry nitrogen fertilizers by contributing its eco-safenutrient stabilizing and ancillary benefits, the large granules areinefficiently not likely to be co-joined next to the granules of theother fertilizers when both are physically mixed together and spreadonto and into cultivated soils. Finally, because the evolving ionicforms can be toxic to seeds and seedlings, a waiting period betweenapplication and planting is often needed, which not only decreases thetime for crop production, but can often result in fertilizer run-offinto streams and rivers. Putting poorly soluble CaNCN hard, non-dustygranules or commercial dusty CaNCN powder into water containing vesselsof urea nitrogen fertilizers to stabilize them causes the carbon andcalcium containing particles to settle as un-sprayable sludge.

SUMMARY

Disclosed herein are fluid ionized compositions, such as fluid calciumcyanamide fertilizer compositions, methods of preparation and usesthereof. The disclosed compositions and methods create and stabilizeactive ionic compounds present in the compositions, such that nutrientscan more effectively be taken up by plants, such as in crops. Thedisclosed compositions and methods facilitate controllable site-directeddelivery of the contents of the ionized, compositions. The compositionsand methods are effective for fertilizing, soil amending, calciumstabilizing leachable heavy metals in soil and metal tank corrosionprevention and freeze protection of the compositions, as well asproviding ionized active calcium for odor and organism inhibition. Thecompositions are stable, easily calibrated, and non-clogging, such thatthey can effectively be used for immediate spray delivery application totarget sites.

In some embodiments, a fluid composition includes a mixture of about 40to 20 parts of dissolved acid or acid-formed nearly neutral pH nitrogenfluid plant nutrient compounds and about 1 to about 5 parts of a mixtureof insoluble or weakly soluble high pH calcium-formed plant nutrientcompounds. In some examples, the dissolved acid includes nitric acid,phosphoric acid, weak carbonic acids or a combination thereof. In someexamples, such as some urea such as in some urea mixing/blendingexamples, the acid-formed nitrogen plant nutrient compounds are insolution and include ammonium nitrate, calcium nitrate, urea ammoniumnitrate, calcium ammonium nitrate, ammonium phosphate, high pH aqueousammonia or combinations thereof. In some examples the insoluble orweakly soluble high pH calcium-formed plant nutrient compounds are insolution and comprise calcium cyanamide (CaCN₂), gypsum (e.g.CaSO₄.2H₂O), calcium carbonate (e.g. CaCO₃), calcium chloride (CaCl₂),potassium chloride (KCl), potassium sulfate (KS) or combinationsthereof.

Methods of using the disclosed compositions include, without limitation,in industry and farming, plant feeding, nutrient stabilization, calciumdecomposition (composting) to deprive odor and disease causing organismstheir food habitat, fertilizing and soil amending, freezing preventionand corrosion prevention. In one example, a method of treating excretais disclosed. In some examples methods of treating excreta can includeadding an effective amount of a disclosed fluid composition to excreta,where the H₂O present in the fluid mixture comprises less or more than14× the mass of the insoluble or weakly soluble high pH calcium formedplant nutrient compounds, thereby forming a mixture of treated excreta.

Methods of enhancing plant growth are also disclosed. In one example, amethod of enhancing plant growth includes applying an effective amountof a disclosed fluid compositions in which the H₂O present in the fluidcomposition comprises at least 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds to soil priorto, during and/or after planting, thereby enhancing plant growth.

Methods of digesting insoluble or weakly soluble high pH calcium-formedplant nutrient compounds to form ionized calcium compounds are alsodisclosed. In some examples, the methods include combining a mixture ofabout 40 to about 20 parts of dissolved acid or acid-formedapproximately neutral pH nitrogen plant nutrient compounds to about 1 toabout 5 parts of a mixture of insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds, where the dissolved acidincludes nitric acid, phosphoric acid, a weak carbonic acid or acombination thereof and the acid-formed nitrogen plant nutrientcompounds are in solution and includes ammonium nitrate, calciumnitrate, urea ammonium nitrate, calcium ammonium nitrate, ammoniumphosphate, high pH aqueous ammonia or combinations thereof whichhydrolyze the insoluble or weakly soluble high pH calcium-formed plantnutrient compounds in solution which can include calcium cyanamide withits free carbon, gypsum, calcium carbonate, calcium chloride orcombinations thereof, thereby forming ionized elements from withincalcium compounds and hydrolysis activated, particle digested carbon.

Also provided are methods of making a fluid composition. In someexamples, a method of making a fluid composition includes combining amixture of about 40 to 20 parts of dissolved acid or acid-formedapproximately neutral pH nitrogen plant nutrient compounds to about 1 toabout 5 parts of a mixture of insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds, where the dissolved acidincludes nitric acid, phosphoric acid, a weak carbonic acid or acombination thereof and the acid-formed nitrogen plant nutrientcompounds are in solution and comprise ammonium nitrate, calciumnitrate, urea ammonium nitrate, calcium ammonium nitrate, ammoniumphosphate, high pH aqueous ammonia or combinations thereof and theinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds are in solution and comprise calcium cyanamide, gypsum,calcium carbonate, calcium chloride or combinations thereof, therebyforming a fluid composition.

The foregoing and other features and advantages of the disclosure willbecome more apparent from the following detailed description, whichproceeds with reference to the accompanying figures.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a bar graph showing the differences over time of the levels ofblack carbon color from calcium cyanamide (CaNCN) carbon in mixedsolutions of urea ammonium nitrate (UAN 32) comprising 20% water andurea in 57% water. Shown in the figure, there is considerably moreinsoluble black carbon suspended for a longer time in the UAN solution,which demonstrates that the disclosed solutions are more saturated withCaNCN ionic elements than in solutions with water.

FIG. 2 is a bar graph comparing the fineness of digested particles.Here, from a strong light being shown through dense carbon blacksolution vessels, it appears that the alkaline aqua ammonia solutionaids acid formed compounds in UAN in digesting insoluble CaNCNparticles. The 75% aqua ammonia solution allows more light throughsooner each time after mixing and some jar shakings, indicating finerparticles.

FIG. 3 is a bar graph that displays the results of CaNCN particle sizereduction measured by passing through two extremely fine screenings,after mixing insoluble CaNCN in the water of the three disclosedfertilizer solutions. Then the effect of a suspension agent in them andthe improved effect from using a venturi by-pass system are shown incolumns 4 and 5.

FIG. 4 is a bar graph showing enhanced CaNCN hydrolysis from as littleas 5% CaNCN disclosed UAN solution, rather than the disclosed 95% addedto 14× water hydrolyzed CaNCN. These bars indicate an increase in thespeeding up of CaNCN hydrolysis by 25% within 15 minutes.

FIG. 5 is a line graph demonstrating the effect of particle hardness andsize related to the speed and completion of CaNCN hydrolysis over time.This differentiates by using CaNCN hardened and enlarged granules of 1.7mm-3.5 mm size compared to disclosed microchip powder of 0.0 to 1 mmsize.

FIG. 6 is a bar graph showing the field corn yield and sugar brix energyincreases of 13% and 33% from fluid 0.5% CaNCN in 99.5% disclosedstabilized UAN 32 over standard fluid UAN 32, in triple replicated fieldcorn nitrogen fertilized studies. These are averages from 60-120-180lbs. nitrogen/acre.

FIG. 7 is a bar graph showing the time degradation effect from disclosedfluid digested calcium containing CaNCN in fluid manures. The operativeis for calcium to remove the undesirable factors of manures by thedigestion of feces and thus, the source of stink odor and harborant foodfor human harmful organisms.

FIG. 8 is a bar graph showing synergistic fertilizer ancillary reducedplant competing weed pressure between pre-plant strawberry fertilizingwith 1.) 750 lbs. hardened granules CaNCN/acre on 5 weed species, 2.)decanted aliquot from making 82 lbs. CaNCN/acre together with 190 lbs.of urea/acre in water on 7 weed species, 3.) disclosed fertilizedcompositions from making 8 lbs./acre CaNCN together with 289 lbs. UAN insolution/acre on 7 weed species. The 8 lbs. was a dramatic, unexpected9× and 94× reduction of CaNCN use and 8 lbs./289 lbs. was 100% alkalineweed seed tissue digestion versus less than 100% from 94× more CaNCN.This was a visually clear demonstration of CaNCN's synergisticcontribution to making soluble and some weakly soluble common fertilizercompounds into the 3^(rd) from left bar's disclosed soluble, plantabsorbable, ionic nutrients solution.

FIG. 9 is a bar graph showing the visual response to freezing overnighttemperature of jarred dilute 0.25% CaNCN in UAN 32. Clearly it displayedthat CaNCN in UAN, reduces the freezing point of commercial UAN 32 downto zero degrees Fahrenheit.

FIG. 10 is a bar graph showing a field corn study yield increases fromCaNCN in fluid UAN compositions at two levels of 0.25% and 0.5%. Thisdemonstrates that 0.25% CaNCN in the present application activatedcarbon is enough for microbes to feed on to hold their nitrogen from99.75% UAN.

FIG. 11 is a bar graph showing the improved nitrogen content in the earleaves of field corn in a study, from 0.5% CaNCN in fluid UANcompositions. This evaluation is standard in determining the fate, ratioand destinations of soil applied nitrogen.

FIG. 12 is a pie chart showing the U.S. nitrogen fertilizer marketshares per annum for both dry and fluid nitrogen fertilizers.

FIG. 13 is a bar graph illustrating the compositions' carbon that feedssoil microbes that feed plant root growth. Thus, such microbe feedingcarbon can be a constant companion with the disclosed ionic plantnutrients, for a synergistic higher level of feeding plant roots.

FIG. 14 displays a UAN foliar phytotoxicity effects summary from ofthree separate non-replicated pansy holed pots with adjacent sod pads ina water holding tray. The UAN desiccated the pansy and adjacent sod pad100%. The carbon containing 5% CaNCN composition lowered pansy and soddesiccation 65%. The near nil 10× diluted 0.5% CaNCN composition, thatwas MDB treated, lowered the pansy and sod desiccation 35%. Therefore,both the carbon and the MDB treatment contributed to lowering UANdesiccation.

FIG. 15 lists two sequential corn and cover crop cropping, their gradingcategories in yield and plant responses, in percentage increases fromcarbon UAN over UAN only.

DETAILED DESCRIPTION OF SEVERAL EMBODIMENTS I. Introduction

Embodiments disclose creating ionized fluid calcium cyanamide withcalcium fertilizer or other calcium containing compounds orcompositions, by combining them with acid based nitrogen or calciumcontaining compounds of other fluid fertilizers, such as fluid UreaAmmonium Nitrate (UAN), Calcium Ammonium Nitrate (CAN), Ammonium Nitrate(AN) or Ammonium Phosphate. The latter are for digesting dry calciumcyanamide particles to sprayable particles and thus speed up itshydrolysis to ionic component solutions where its carbon-is digested tofiner, much larger surface area, particles that may be graphene,reported as a possible silicon replacement memory tool, or other carbonallotropes that are easily suspended or solutionized. An electrolyticsuspension agent may be added to assure the carbon's suspension. Simpleblending and no added heat is needed.

Surprisingly, without the disclosed fluids' degradation, a full spectrumof additional plant nutrients may be added to water or water containingfluid manures into which such nutrients may be added, where thedisclosed composition processes further digest the particles of thoseadditives where the CaNCN or added particles do not harden together andsettle. This process affords fluid blending fertilizer dealers to nolonger need the energy for heat to dissolve urea to attain higher fluidurea nitrogen analysis.

The compositions reduce the crystallization freezing points of saturatednitrogen fluids (UAN 32) from 32° F. down to below about 0.0° F. Thisreduces the need, in colder climates, to reduce UAN 32 down to UAN 28 toreduce UAN's freezing point down to 1° F. The compositions raise theneutral pH of UAN to above 7.8 to essentially eliminate UAN tank welds'cracking ferrous corrosion (Wilson, Fodor, Kenton U.S. Pat. No.4,239,522), without standard UAN corrosion inhibitors such as chromate,dichromate or phosphorus ions.

CaNCN/UAN has demonstrated to dramatically reduce CaNCN particle sizesto immediately sprayable sizes as compared to urea in water andnon-calcium cyanamide/UAN. Today, UAN, which is suitable for combinedpesticide applications, is evermore becoming the choice nitrogenfertilizer. As herein disclosed, calcium cyanamide stabilized UAN caneasily be made by fluid fertilizer dealer blenders, for cleaner waterwatersheds one watershed at a time. Annual use statistics for U.S. fluidnitrogen fertilizers are 12,000,000 tons/annum for UAN, 6,000,000tons/annum for dry urea and 4,000,000 tons/annum for compressed gasammonia.

In corn replicated field studies, a microchip (1 mm) of calciumcyanamide, pre-hydrolyzed in 300° F. moist hot urea factory melted ureato become a pre-hydrolyzed CaNCN seed inside each urea granule alwaysincreased yields to an average over urea of 11%, over 8 years, in bothwet and dry years and reached surprisingly lower nitrogen to higheryield ratios for greater nutrient use efficiency (NUE). This lowersnitrogen use and thus less exposure for loss to ground waters andrelease of ozone suspect nitrous oxide gas to air.

It would be very desirable for the public and farming practices to havepre-hydrolyzed, immediately sprayable/injectable, fluid ionic plantnutrients from fines and granules of calcium cyanamide, to stabilizepollution suspect, but lower cost, fluid common fertilizers and manureswhere the combined comprise carbon fed soil microbes' that holdotherwise leachable, to non-leachable, nitrogen and phosphate that feedsplants and soil microorganisms in an eco-safe manner, until plant roothairs need them including other macro and micro plant foods in solublesolution forms that may be co-applied for them all to comply withenvironmental pollution laws where the nutrients all go into plants sothey are not before, during and after season-exposed to leaching intoground waters.

Although calcium cyanamide is defined as a nitrification inhibitor(AAPFCO N-12 vol. 57), the present application discloses that hydrolyzedactive carbon feeds soil microbes which hold nutrients in the soil toattain the AAPFCO definition effects, which are where low percentages ofCaNCN fertilizer can prevent nitrogen and phosphate plant foodcomponents from being lost to leaching into ground waters before theplants can use them all up.

Nearly immediately, after high pH in water CaNCN (12.2 pH) is in moistsoil below 10 pH, the hydrolyzed acid HNCN dimerizes to dicyanamide(DCD) which is a nitrogen only stabilizer DCD, that is exempt frompesticide regulation.

Over numerous corn field studies (12 years), the inventor discoveredthat as little as a 0.25% calcium cyanamide additive to UAN can speed upcommon granular and fluid nitrogen fertilizer plant uptake and in doingso prevent pollution and increase crop yields in ranges from 5-13% andsugar energy 33%, and thus well pays for and gets multiples of dollarreturns (ROIs) in yields from disclosed otherwise costly high rates ofcalcium cyanamide fertilizer alone. Calcium cyanamide prevention ofnitrogen (N) and phosphorus (P) loss to ground waters, instead goinginto corn kernel food and energy yields, was expressed by at-harvesthigher corn ear leaf N.

In a station field corn study, it was determined that calcium cyanamidepowder at as low as 0.25% in UAN increased average yields 13% over UANonly, at down to 66% less nitrogen. In a similar study-the carbonUAN-average-corn plant chlorophyll was increased 9% with again lessnitrogen than UAN alone. Chlorophyll, the plant's means to absorb andconvert sun energy to starch energy, is related to plant conversion tosugar energy.

Nitrate (NO³) N in UAN is reported to rob plants of energy for theplants to convert it to plant useable NH₄ N. High sugar brix energy cornis important in increasing corn biofuel yields. In the field cornstudies of microbe held N fertilizers, along with other recent farminnovations, yielded up to 150 gallons more biofuel per acre whileproducing 2.8× more food from corn on today's corn acres, overnon-calcium cyanamide stabilized N. Calculated, this made-in-USA energyand not buying foreign fossil energy at $2.50/gallon gasoline adds up to½ $trillion/annum stimulus for U.S. jobs and treasuries economy. Sweeter(more energy) food and feed is preferred by humans and naturally byanimals. And, such healthier plants express natural plant immunityresistance against plant antagonists.

During the corn studies, simultaneously in California strawberryculture, the inventor attempted to add dry calcium cyanamide tofluidized urea containing 14× water. However, it plugged valves andscreens. A successful decant filtering system was implemented, but itleft solid hardened cakes of soil-valuable carbon and plant valuablecalcium in near insoluble form to be separately discarded in piles.

The decant CaNCN/urea aliquot in irrigation delivery systems proved todisplay the same traits in strawberries as in corn, but at high dilutionaliquot rates. Pre-planting, in its high pH created soil made italkaline tissue digestion unfavorable to young plant root antagonistsand competing plants, for less young plant pressures. In sequentialpost-plant drip irrigations it sequentially, via contributing a highercarbon/nitrogen ratio instead of nitrogen only, created uniformblossoming and picks which increased strawberry yields. And one studyshowed curing calcium deficiency in an unheard of brief period of 3days. These aspects increased mid-season strawberry yields over standardpractice costly slow release fertilizer and costly soil cleaning, ozonesuspect, methyl bromide gas. Low cost fast release common fertilizer inthese plots had best results over high cost slow release fertilizer.Together, these features can save the California strawberry industrygreater than $100,000,000/annum.

Unanticipated, a Greenfield Calif. two years pre-plant strawberry bedtriple replicated studies demonstrated the superiority of carbonstabilized UAN over carbon/calcium sludge drop out below decant aliquotstabilized urea in irrigation water systems. In these studies, thereduced weed pressure from 50 lbs. of nitrogen/acre from calciumcyanamide carbon stabilized UAN exceeded such response from 100 lbs. ofnitrogen from stabilized aliquot CaNCN/urea. This suggested that UAN wasa much more active companion to calcium cyanamide than urea. This callsattention to ammoniated nitric acid ammonium nitrate added to urea inUAN being the operative in improved calcium cyanamide hydrolysis fromits UAN particle digestion in the present disclosure disclosed ionicstates, which enhances urea hydrolysis to gaseous ammonia in water,that's associated with high pH alkaline tissue digestion.

Agriculture farm watersheds that need stabilized nitrogen, such asMidwestern agriculture farm watersheds, are dependent upon rain waterand therefore do not have irrigation options to precision deliverfertilizers to those plants. One option was to blend calcium cyanamideand urea into water and directly spray/shank/inject onto/into cropsoils. However, in spite of many suspension agent jar tests, often thisstill led to calcium cyanamide plugging of sprayer screens. In theMidwest this proved that short time water residence did not dissolvecommercial calcium cyanamide's larger solid sizes. Expensive re-shippingof on hand stock to expensive milling/blending and re-packagingprocesses to make uniform fine sprayable calcium cyanamide powder solidsbecame the only solution. Such uniform powder in water did not stayfully suspended for an hour and had to be pre-circulated to attainuniform field applications.

About 300 jars were used in testing the addition of various agents towater to attain calcium cyanamide screen passage and suspension throughscreen sizes used in sprayers, such as 80 mesh and finer up to 200 mesh.None were successful. Heating aided this somewhat, but notsatisfactorily.

Surprisingly, commercial calcium cyanamide poured into jars of fluid UAN32 and shaken allowed all the solids to pass through 80 and 100 meshscreens and even 200 mesh screens. That suspension lasted over 3 hours.Nozzle plugging was not experienced in any of the studies when CaNCN wasmixed into jars of UAN.

Further jar tests revealed that similar action to UAN 32 was attained influid AN 20 and CAN 17. This demonstrated that it's the ammonium nitrateor reformed nitric acid that likely caused the increased calcium incalcium cyanamide particle digestion to enhance hydrolysis to disclosedionic fluid calcium cyanamide compositions.

All previous jar tests with calcium cyanamide dissolved in water or aquaammonia created near immediate settlements of large black particles ofcalcium cyanamide.

The solution to the this dilemma turned out to be to first make aconcentrate of 5% calcium cyanamide in UAN. Then dilute it by pouringthat concentrate into dissolved urea in water (Urea 20) or ammonia inwater (Aqua 20) to 10× dilution (0.5% calcium cyanamide) needed to holdthe soil nitrogen when using the latter two. Thus, the latter two haduniform fluid ionized calcium cyanamide throughout that lasted for days.

The only drawback of not using UAN is the lack of urea hydrolysis in UANthat contributes to the disclosed high pH alkaline digestion.

Gaseous ammonia (NH₃) fertilizer is typically injected deep into soil toprevent its gaseous escape in Midwest field crop culture, rather thanthe disclosed strawberry bed top spray and sprinkle method or in dripirrigation water methods to create the disclosed water alkalinedigestion of protein matter on bed surfaces.

UAN's urea digested to ammonia essentially resulted in aqua ammonia.However it is not atmospheric or human ammonia exposure allowed inclosely inhabited strawberry culture whereas, safe urea in water or UANis well accepted for topical soil application. It can be bed top sprayedand sprinkle irrigated or precision placed in precision placedirrigation water to un-cropped or cropped soils, it was discovered thatirrigation water traps the ammonia even better than plastic tarping forcontrolled soil conversion to harmless soil attaching ammonium (NH₄)fertilizer. There's no irrigation in Midwest field crops culture.

Additional jar studies revealed that when a powerful light was putagainst the jar of the black calcium cyanamide suspension, right aftercombining the two, one could see a black pillowing or blooming effect,like a volcano erupting. Black calcium cyanamide in water with dissolvedurea never showed such effect. This suggested that ammoniated nitricacid ammonium nitrate added to urea in UAN likely caused the digestingof the non-uniform black calcium carbonate solids. Powder calciumcyanamide in UAN made uniform tiny micro particles that passed througheven the smallest screen sizes. Thus, these fine particles hydrolyzedfaster to CaNCN ionic macro and micro nutrient ions, uniformlysaturating its UAN diluent, displayed by longer floating of CaNCN'sotherwise insoluble carbon. This demonstrated that the solution mixtureswere likely all in solution far longer than imagined possible, or asblack carbon displayed at least 300% longer than water only. In asubsequent commercial venturi by-pass MDB test run carbon stable-UAN,without suspension agent stayed completely black for weeks, with maximum25% reduction in the black level for months, suggesting the alterationwas permanent.

CaNCN (0.025% to 0.05%) added to UAN indicated that compounds withincommercial CaNCN became fully ionic elements. Surprisingly, theconcentrate UAN digestion process, in jars after 12 hours, displayed ayellow aliquot visually showing the hydrolyzing of calcium cyanamide's2.5% considered insoluble calcium sulfate, (gypsum) micro nutrient toionic sulfur ion elements, for immediate plant uptake. This supportedthe supposition that the UAN digestion of calcium cyanamide assured thefull hydrolysis of all calcium cyanamide compounds into their ionicelements. Thus, finished disclosed compositions with added nutrientcompounds likely all comprise fully plant soluble ionic elements in thedisclosed compositions.

This means that plant root hairs, which can only take in or let outtheir nutrients by osmosis from osmotic pressure variances throughsemi-permeable membranes, going from hypertonic to hypotonic to staticisotonic states inside the root hair cells, are more likely to takethose in if as in disclosed solution compositions they primarilycomprise ions rather than dissolved compounds. See disclosed figures andtables 6 (Sugar Brix), 10 (Yield Increases) 11 (Ear Leaf N). Osmoticpressures are associated with water of crystallization and lowering offreezing points of solutions (Jacobus H. van't Hoff; Osmotic pressureand chemical equilibrium; Nobel Lecture, Dec. 13, 1901) See disclosedfigures and Table 9 (Freezing). The disclosed figures and tablesdemonstrate un-obvious enhanced responses compared to soil fertilizationwith common fertilizer compounds and lowered freezing points of thedisclosed composition solutions.

Also, the disclosed compositions are more likely to assure plantnutrient element assimilation of micronutrients in soluble ionic formsin soil solutions from fluid calcium cyanamide/UAN compositions(nitrogen, calcium, iron, silicon, aluminum, magnesium, nickel, sulfur).Adding the disclosed compositions to animal digested fluid excretamanures will do the same with their animal digested phosphate, potashand contained micronutrients. And, calcium cyanamide digested excretawill add a new array of broad spectrum, digested organics andmicronutrients contained, ionic composition fertilizers.

Ionic calcium cyanamide components in water depend on its hydrolysis. Inthe disclosed study 5% UAN was added to calcium cyanamide in 14× water.5% UAN increased calcium cyanamide hydrolysis toward its theoreticalionic cyanamide nitrogen yield by 25% over water only within 15 minutes.An additional laboratory water study took one hour to reach 90% oftheoretical cyanamide nitrogen yield. The disclosed study was intendedto determine if UAN increased hydrolysis time to cyanamid (NCN) overwater only. If as here disclosed the mixtures were 95% UAN (comprising20% water) and 5% calcium cyanamide it is expected that the fullhydrolysis to full theoretical cyanamide yield would be within or muchless than 15 minutes, based on disclosed discovered “volcano eruption”like action, from 5% calcium cyanamide/95% UAN.

In a subsequent study, a 200 gallon UAN/5% CaNCN concentrate wasprepared using a commercial fertilizer blending system that comprised aventurii MDB by-pass system for inductions. Non-uniform calciumcyanamide solids were inducted into MDB venturi circulating UAN. Theresulting concentrate stayed in near full suspension/dilution for weeks.Slight jar tipping disturbance made it go back into apparent fullsuspension/dilution solution. An added electrolytic suspension agentnever before displayed such micro black insoluble carbon particles tostaying in full suspension, indicating indefinitely.

This means that calcium cyanamide can become fluid calcium cyanamide. Aconcentrate of that was diluted in water and fluid manures withoutcaking and where the dilute comprised all the calcium cyanamidecomponents and its nutrient compounds into rapidly plant absorbable,soluble ionic forms. Recently, jar tests of fluid AN (Ammonium Nitrate)and fluid CAN (Calcium Ammonium Nitrate) displayed the same as UAN orbetter.

Calcium cyanamide in water initially reaches 12.2 pH. Calcium cyanamideadded to UAN as a concentrate moves to a pH of 9.5. At equilibrium itbecomes 8.5 pH. 0.25% calcium cyanamide sustains a pH of 8.5. Wilson,Fodor, Kenton (U.S. Pat. No. 4,239,522) claim that a pH of at least 7.8is sufficient to substantially eliminate ferrous corrosion. Today UAN28-32 older storage tanks' weld cracking is a top level of EPA pollutionand OSHA accident concerns.

In the winter, jars of suspension agent calcium cyanamide/UAN 32compared to UAN 32 only were left outside overnight at below freezingtemperatures. The calcium cyanamide jars had no crystals in them thenext morning, compared to 90% crystals UAN jars where these crystalswould not pass through a gauze mesh but the CaNCN/UAN full passedthrough the gauze. This was extended in a freezer where the samecomparative results were demonstrated down to 0° F. This can becomemajor economic storage and shipping savings.

The disclosed compositions are associated with a number of advantagesincluding, but not limited to, the following: (1) mitigate thelimitation of UAN composition freezing points; (2) mitigate UAN metaltanks corrosion; (3) speed the hydrolysis of calcium cyanamidehydrolysis to ionic nutrient forms; (4) increase the delivery time anduptake of nutrients into plants of ionic calcium cyanamide and combinedmacro and micronutrients in carbon stabilized UAN compositions; (5)increase plant sugar production from UAN N; (6) increase calciumcyanamide inside UAN plant yields over UAN only; (7) have a venturi, MDBcirculation or the like, in fluid fertilizer blending plants whilecirculating UAN to attain calcium cyanamide micro particles status toattain stabilized UAN in long suspension/solution states; (8) have UANspeed up hydrolysis and particle digestion of calcium cyanamide, (9)have UAN hydrolysis assure the delivery of all calcium cyanamide andcombined nutrient sources, including fluid manures, in ionic states;(10) have ammonium nitrate added to urea in UAN which enhances thedigestion of calcium cyanamide particles over urea only; (11) havecalcium cyanamide inside UAN to increase nutrient use efficiency (NUE)more than with urea; (12) where calcium cyanamide/UAN solves the issuesincurred in pre-hydrolyzing calcium cyanamide in water before usages,such as losing calcium and carbon to waste piles from near immediatesettlement of calcium cyanamide solids into hard cakes of carbon andnear insoluble calcium carbonate; (13) where UAN solves clogged valvesand screen problems that prevent immediate spraying in water of calciumcyanamide stabilized fertilizers and fluid manures; (14) where UANeliminates expensive milling/blending/re-packaging of factory grade oversize particles to prepare commercial calcium cyanamide for into watermixtures; (15) where UAN extends the time of calcium cyanamide insolution and or suspension; and (16) where UAN and agents create a basefluid stabilized composition suitable to add any numbers of plant foodnutrients to deliver a full spectrum of ionized plant food elements inone fluid solution. The disclosure's increased plant responses to thedisclosed fluid ionized compositions also indicates that calciumcyanamide nitrogen microbe stabilization can result from microbes morerapidly consuming the disclosed soluble, likely molecular, carbon formand absorbing the disclosed nitrogen composition's nitrogen for laterrelease as plant roots consume the decayed microbes' containing nitrogen

II. Overview of Several Embodiments

Disclosed herein are fluid ionized compositions, such as fluid calciumcyanamide fertilizer compositions, methods of preparation and usesthereof, including, without limitation, in industry and farming, plantfeeding, nutrient stabilization, decomposition (composting), odor andorganism inhibition, fertilizing and soil amending. In some embodiments,a fluid composition includes a mixture of about 40 to 20 parts ofdissolved acid or acid-formed approximately neutral pH nitrogen plantnutrient compounds and about 1 to about 5 parts of a mixture ofinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds, where the dissolved acid comprises nitric acid, phosphoricacid, a weak carbonic acid or a combination thereof and the acid-formednitrogen plant nutrient compounds are in solution and comprise ammoniumnitrate, calcium nitrate, urea ammonium nitrate, calcium ammoniumnitrate, ammonium phosphate, high pH aqueous ammonia or combinationsthereof; and the insoluble or weakly soluble high pH calcium-formedplant nutrient compounds are in solution and comprise calcium cyanamide,gypsum, calcium carbonate, calcium chloride, potassium chloride,potassium sulfate or combinations thereof, and microbe nutrient freecarbon.

In some embodiments, a disclosed composition includes dissolved acid oracid-formed approximately neutral pH nitrogen plant nutrient compoundsincluding a urea ammonium nitrate (UAN), where the UAN solutioncomprises about 30% to about 35% urea, about 40% to about 45% ammoniumnitrate with the residual as H₂O; and the insoluble or weakly solublehigh pH calcium-formed plant nutrient compounds are in solutionscomprising H₂O that contain calcium cyanamide. In some embodiments, theH₂O present in the fluid mixture comprises less than 14× the mass of theinsoluble or weakly soluble high pH calcium formed plant nutrientcompounds in the mixture. In some embodiments, the H₂O present in thefluid mixture comprises at least 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds in the mixture.

In some embodiments, a disclosed composition includes about 5 percent toabout 10 percent by weight calcium cyanamide, such as about 7 percent toabout 8 percent by weight calcium cyanamide.

In some embodiments, a disclosed composition further includes excreta,such as liquidized manure. In some embodiments, the excreta is dairy.

In some embodiments, the disclosed composition includes from about 0.01percent calcium cyanamide to about 99.99 percent UAN solution and fromabout 0.1 percent to about 99.9 percent fluid excreta.

In some embodiments, the disclosed composition includes about 25 percentcalcium cyanamide, about 75 percent UAN solution and from about 25percent excreta.

In some embodiments, a disclosed composition includes at least onenon-nitrogen material to the mixture, such as a plant nutrient. In someembodiments, the non-nitrogen material includes phosphorous, potassium,iron, copper, zinc, manganese, boron, magnesium, molybdenum, sulfur,nickel, and mixtures thereof.

In some embodiments, a disclosed composition includes an electrolyticsuspension agent, such as aniline or nigrosine or carbon black ionicsubstances or ionized metal elements, such as silicon, iron, aluminum,carbon or a combination thereof.

In some embodiments, the approximately neutral pH nitrogen plantnutrient compound mixtures include a pH of about or above 7.8 and 7.9.

In some embodiments, a disclosed composition includes particles with anabout 200 mesh screen pass through.

In some embodiments, a method of treating excreta includes adding aneffective amount of a disclosed fluid composition to excreta, where theH₂O present in the fluid mixture comprises at least 14× the mass of theinsoluble or weakly soluble high pH calcium formed plant nutrientcompounds, thereby forming a mixture and treating excreta.

In some embodiments, the excreta is liquidized manure. In someembodiments, the excreta is not limited to, dairy.

In some embodiments, the method further includes adding at least onenon-nitrogen material to the mixture, such as a plant nutrient. In someembodiments, the non-nitrogen material is selected from the groupconsisting of phosphorous, potassium, iron, copper, zinc, manganese,boron, magnesium, molybdenum, sulfur, nickel, and mixtures thereof.

In some embodiments, the method further includes adding an electrolyticsuspension agent to the mixture, such as an ionized metal element, suchas silicon, iron, magnesium, nickel, aluminum, carbon or a combinationthereof.

In some embodiments, the approximately neutral pH nitrogen plantnutrient compound mixture has a pH of or above about 7.8 and 7.9.

In some embodiments, the fluid composition used to treat the excretacomprises particles of with an about 60 to about 100 mesh pass throughscreen size, such as about 80 to about 100 mesh pass through screensize.

In some embodiments, the method of treating excreta further includesapplying the mixture to soil by spraying.

In some embodiments, a method of enhancing plant growth includesapplying an effective amount of a disclosed fluid composition in whichthe H₂O present in the fluid composition comprises at least 14× the massof the insoluble or weakly soluble high pH calcium formed plant nutrientcompounds to soil prior to, during and or after planting, therebyenhancing plant growth.

In some embodiments, applying an effective amount comprises applying thecomposition by spraying, shank soil injection or into sprinkler or dripirrigation.

In some embodiments, a method of making a fluid composition includescombining a mixture of about 40 to 20 parts of dissolved acid oracid-formed approximately neutral pH nitrogen plant nutrient compoundsto about 1 to about 5 parts of a mixture of insoluble or weakly solublehigh pH calcium-formed plant nutrient compounds, where the dissolvedacid includes nitric acid, phosphoric acid, a weak carbonic acid or acombination thereof and the acid-formed nitrogen plant nutrient compoundare in solution and comprise ammonium nitrate, calcium nitrate, ureaammonium nitrate, calcium ammonium nitrate, ammonium phosphate, high pHaqueous ammonia or combinations thereof and the insoluble or weaklysoluble high pH calcium-formed plant nutrient compounds are in solutionand comprise calcium cyanamide, gypsum, calcium carbonate, calciumchloride or combinations thereof, thereby forming a fluid composition.

In some embodiments, the method of making a fluid composition is one inwhich the dissolved acid or acid-formed approximately neutral pHnitrogen plant nutrient compound is a urea ammonium nitrate (UAN), wherethe UAN solution comprises about 30% to about 35% urea, about 40% toabout 45% ammonium nitrate with the residual as H₂O; and the insolubleor weakly soluble high pH calcium-formed plant nutrient compounds are insolution comprising H₂O and include calcium cyanamide.

In some embodiments of the method of making, the H₂O present in thefluid mixture includes less than 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds in the mixture.

In some embodiments of the method of making, the H₂O present in thefluid mixture comprises at least 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds in the mixture.

In some embodiments of the method of making, the combining is performedin the presence of a circulation process, such as a venturi by-pass MDBcirculation system.

In some embodiments, the method of making further includes adding atleast one non-nitrogen material to the composition, such as a plant ormicrobe nutrient.

In some embodiments, the non-nitrogen material is selected from thegroup consisting of phosphorous, potassium, iron, copper, zinc,manganese, boron, magnesium, molybdenum, sulfur, and mixtures thereof.

In some embodiments, the method of making further includes addingexcreta to the composition, such as liquidized manure. In someembodiments, the excreta is dairy excreta.

In some embodiments, the method of making is performed in an openedcontainer.

In some embodiments, the method of making is performed in an unsealedcontainer.

In some embodiments, the method of making is performed in the presenceof atmospheric CO₂.

In some embodiments, the method of making further includes dehydratingthe fertilizer composition to form a solid.

In some embodiments, a method of digesting insoluble or weakly solublehigh pH calcium-formed plant nutrient compounds to form ionized calciumcompounds includes combining into a mixture of about 40 to about 20parts of dissolved acid or acid-formed approximately neutral pH nitrogenplant nutrient compounds to about 1 to about 5 parts of a mixture ofinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds. Then the dissolved acid comprising nitric acid, phosphoricacid, a weak carbonic acid or a combination thereof and the acid-formednitrogen plant nutrient compound are in solution and comprise ammoniumnitrate, calcium nitrate, urea ammonium nitrate, calcium ammoniumnitrate, ammonium phosphate, high pH aqueous ammonia or combinationsthereof and hydrolyze the insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds in solution which comprisecalcium cyanamide, gypsum, calcium carbonate, calcium chloride orcombinations thereof, thereby forming ionized calcium compounds andinsoluble carbon.

In some embodiments of the method of digesting, the mixture of insolubleor weakly soluble high pH calcium-formed plant nutrient compoundsincludes calcium cyanamide.

In some embodiments of the method of digesting, the combining isperformed in the presence of a circulation process, such as a venturiby-pass system.

III. Abbreviations and Terms a. Abbreviations

F: Fahrenheit

N: nitrogen

NUE: nutrient use efficiency

P: phosphorus

Tons/a: tons per acre

UAN: urea ammonium nitrate

CaNCN calcium cyanamide

b. Terms

The following explanations of terms and methods are provided to betterdescribe the present disclosure and to guide those of ordinary skill inthe art in the practice of the present disclosure. As used herein and inthe appended claims, the singular forms “a” or “an” or “the” includeplural references unless the context clearly dictates otherwise. Theterm “or” refers to a single element of stated alternative elements or acombination of two or more elements, unless the context clearlyindicates otherwise. As used herein, “comprises” means “includes.” Thus,“comprising A or B,” means “including A, B, or A and B,” withoutexcluding additional elements.

Unless explained otherwise, all technical and scientific terms usedherein have the same meaning as commonly understood to one of ordinaryskill in the art to which this disclosure belongs. Although methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the present disclosure, suitable methods andmaterials are described below. It is further to be understood that anyquantitative values are approximate whether the word “about” or“approximately” or the like are stated or not. All percentages andratios are calculated by weight unless otherwise indicated.

Acid-Formed Approximately Neutral pH Nitrogen Plant Nutrient Compound:

A phrase to include compounds including ammonium nitrate, calciumnitrate, urea ammonium nitrate, calcium ammonium nitrate, ammoniumphosphate, high pH aqueous ammonia or combinations thereof.

Ammonia:

A compound of nitrogen and hydrogen with the formula NH₃. Ammonium isthe ionized form of ammonia and has a formula of NH₄. In someembodiments, a disclosed composition includes ammonia and or ammonium,such as ammonium nitrate, calcium nitrate, urea ammonium nitrate,calcium ammonium nitrate, ammonium phosphate, high pH aqueous ammoniawith or without additives or combinations thereof. Additionally, wherehigh pH ammonia in water digestion breaks down moist living or deadorganic matter, as disclosed, it can result in the disclosed plantmatter effects.

Calcium:

Calcium ions (Ca²⁺) are present in most organic matter and are necessaryfor many enzymatic reactions, including those that facilitate energy useby living organisms such as microbes. Furthermore, calcium ions aid insoil reclamation by flocculating soil and permitting water percolation.Additionally, calcium tends to enhance the breakdown of organic orcarbon matter through these and other actions.

While calcium ions are abundant in nature in naturally occurringlimestone (calcium carbonate, CaCO₃), they are not readily available foruptake because of the relative insolubility of calcium carbonate. Fromthis is seen the need to stabilize calcium ions in soluble form toenhance the speed of calcium uptake into organic matter, both living anddead, to aid plant growth and soil reclamation. In some examples, thedisclosed compositions include calcium.

Calcium Cyanamide (CaNCN):

A composition including about 44% calcium and about 24% nitrogen andabout 12% carbon was first made in the late 1800s, as part of a searchfor a high analysis nitrogen source for industry and agriculture toreplace low analysis (1-<12%) excreta deposits. It is produced in 1000to >3,000° C. electric arc furnaces by burning black coal and whitelimestone in the presence of atmospheric nitrogen. Energy costsrepresent the bulk of calcium cyanamide production costs. Calciumcyanamide is also referred to and synonymous with lime nitrogen (LN);the term lime nitrogen or calcium cyanamide can be used interchangeably.

Commercial CaNCN also known as Nitrolime is actually a mixture ofseveral components formed during or remaining after production of thedesired calcium cyanamide compound. Additional components found incommercial calcium cyanamide include calcium oxide (CaO), graphitecarbon (C), dicyandiamide [(HNCN)₂] and oxides of iron, aluminum,magnesium, nickel, silicon and calcium sulfate (CaSO₄).

As used herein, the term calcium cyanamide is synonymous with the termcommercial calcium cyanamide, its components and itshydrolysis/dissolution products, unless it is clear from the contextthat the compound calcium cyanamide itself is intended. However, itshould be recognized that the terms calcium cyanamide and commercialcalcium cyanamide encompass calcium cyanamide materials where additionalcomponents of commercial calcium cyanamide such as carbon, calciumoxide, dicyandiamide are absent, subject to components derived fromcomponent lime, or are present in amounts different from typicalcommercial calcium cyanamide. These terms also encompass calciumcyanamide materials that have additional nitrogen-containing compoundsand/or non-nitrogen plant nutrients. Furthermore, it should beunderstood that certain embodiments of the composition and method of thedisclosure may be utilized to activate and stabilize the products ofwater dissolution of the individual components typically found incommercial calcium cyanamide, including, for example, dicyandiamide.

Typically, for one reason or another, commercial calcium cyanamide istreated to alter the form of cyanamide or remove components remainingafter manufacture. For example, because calcium cyanamide is a slowacting fertilizer that is sparingly soluble in water, it is oftenfactory converted to water-soluble molecular cyanamide (H₂NCN), which isfaster acting and a higher analysis source of nitrogen. In this process,calcium cyanamide is forced to dissolve in water by precipitation ofcalcium ions (Ca²⁺) as calcium carbonate (CaCO₃) and by acidification toconvert initially formed cyanamide ions (HCN²⁻) into acid cyanamide ion(HNCN⁻) and then into molecular cyanamide which predominates at a pH of4.5-5.5. Insoluble calcium carbonate and graphite carbon, which may beentrained in the calcium carbonate, are then removed by filtration. Theresulting solution must be kept cool, for example, refrigerated, becauseit is unstable above about 70° F.

Because calcium cyanamide is slow acting, one application at a rate ofup to 100 to 3000 lbs./acre lasts all growing season long. However, whencalcium cyanamide is applied at these typical season long rates,particularly in cool and or dry conditions, it is necessary to delayplanting until the high concentrations of plant penetrating initialhydrolysis products of calcium cyanamide, which are toxic to seeds andseedlings (phytotoxic), dissipate. Furthermore, because calciumcyanamide in its noxiously dusty irregular granule form is difficult tocalibrate, its application may be haphazard so that one part of a fieldmay be ready for planting while others exhibit persistent phytotoxicity.The phytotoxic characteristics of calcium cyanamide also make evenrepeated dry applications at lower rates impractical.

For the reasons above, use of dry calcium cyanamide has decreased, andpresently it is no longer used as only a fertilizer or for no longertoday claims as pesticide in the United States. Worldwide, its' use islargely restricted to rice cultivation, where hot, wet conditionsquickly degrade and remove other nitrogen fertilizers, such as urea,from the soil.

Calcium cyanamide is more typically converted to faster acting andhigher analysis forms of nitrogen. For example, calcium cyanamide may beaerobically hydrolyzed in the presence of carbon dioxide to providecalcium free urea (42% N). Other high analysis nitrogen forms which areproduced from calcium cyanamide include calcium free, dicyandiamide((HNCN)₂, 66% N) and molecular cyanamide (H₂NCN, 66% N). These formshave found use in both agriculture and the production of many of today'sindustrial polymer chemicals and medicines. However, plant beneficialcalcium is not a part of these products.

It would be a benefit to provide compositions and methods that exploitthe slow acting nature of calcium cyanamide yet provide immediatelyavailable plant nitrogen and calcium without phytotoxic consequences. Italso would be a benefit if such compositions and methods made it easierto calibrate applications of calcium cyanamide and facilitate repeatedsmaller applications throughout the growing season. Furthermore, itwould be an advantage if these benefits were achieved at more economicalrates of application and enabled more of the components that exist incommercial calcium cyanamide to be utilized.

These benefits have been partially realized by Hartmann, as described inU.S. Pat. Nos. 5,698,004, 5,976,212, and 7,785,388 B2, which areincorporated herein by reference. Contrary to teachings againstfertilizing plants with the initial hydrolysis products of calciumcyanamide (because of their phytotoxicity), Hartmann has worked toprovide easily deliverable, stable, hydrolyzed ionic CaNCN solutions,containing plant penetrating acid cyanamide anions directly to plants.Caustic can be added to such ionic solutions to maintain a pH thatfavors the acid cyanamide ion. The calcium cyanamide solutions taught inthese prior patents are sprayable if insolubles, such as calciumcarbonate and residual carbon, are removed by a means of filtration.Balls and clumps of calcium carbonate that entrain otherwise sprayablecarbon tend to plug pumping and spraying equipment. Because carbon isalso beneficial to plants, microorganisms and soils it would beadvantageous if methods existed to prevent formation of balls and clumpsof it, so that more calcium remained soluble, filtration wasunnecessary, and the residual insoluble carbon found in commercialcalcium cyanamide could be maintained in an easily sprayable form,because even some sprayables are not easy to spray without adjutants andor more water. Furthermore, it would be a benefit if it were possible tomaintain a pH favorable to acid cyanamide ions without having to addcaustic to overcome the tendency of these solutions to drop in pH andform dicyandiamide within pH range between 8 and 10.

When calcium cyanamide first hydrolyzes in water it produces calciumions (Ca²⁺) and cyanamide ions (HCN²⁻) as products. The cyanamide ion isvery basic and reacts with water to form the acid cyanamide ion (HNCN⁻).The acid cyanamide ion is amphoteric, i.e. it can act as either an acidor a base. If the acid cyanamide ion acts as an acid it will revert tothe cyanamide ion, and if it acts as a base it will react to formmolecular cyanamide (H₂NCN). The form that cyanamide takes in solutionwill depend upon the pH of the solution, but molecular cyanamide isfavored at pHs below 10.3, which are typical of soils. Molecularcyanamide may then undergo hydrolysis to form dicyandiamide (C₂H₄N₄) andthen urea, which may further react to form volatile ammonia and thenammonium molecules, which may further be converted to nitrate.

As stated previously, the acid cyanamide ion is plant and organismpenetrating. Once absorbed by plants, the acid cyanamide ion lasts only2-4 hours before it forms urea, which lasts 4-8 hours. Both urea andacid cyanamide stimulate plant arginine production in plants, which isrelated to plant health (see for example, Kunz et. al., Zeitschrift furPlantzen Krankheiten und Flanzenschutz, 61: 481-521, 1954; Lovatt et.al., Proceedings California Plant and Soil Conference 1992 & 1995;Wunsch et. al., Zeitshrift fur Pflanzenphysiology, 72: 359-366, 1974;and Von Fishbeck et. al., Zeitschrift fur Planzen Krankheiten, 71:24-34, 1964). Therefore, compositions and methods that stabilize andprovide urea and acid cyanamide ions to plants-are desirable-towardproducing fruitful, parasite-free, disease-free, healthy plants. Forexample, recently discovered, aphids and other sucking insects have nopancreas to convert sugar, therefore they die. The inventor applieddisclosed CaNCN solution sprays on plants or in the soil and observedthick, brighter shinier leaves that remain fungus and insect free.

When CaNCN is applied at fertilizer rates, atop warm, wet soil, rapiduncontrollable aerobic hydrolysis occurs, moving initially solublecalcium to insoluble calcium forms and cyanamide ions to urea, then todicyandiamide, and then to urea and then to gaseous ammonia at thatlocation. A need is thus seen to economically stabilize initialpre-hydrolysis soluble acid cyanamide ions and calcium ions in highdilutions so that they can rapidly percolate to target sites of choicewhere the ions can be absorbed by plants and aid in maintaining soilporosity.

Dissolved Acid:

An acid in solution. In some examples, a disclosed fluid compoundincludes a dissolved acid, such as nitric acid, phosphoric acid, a weakcarbonic acid or a combination thereof.

Excreta:

Waste matter discharged from the body. In some examples, excreta ismanure, such as liquidized manure.

Gypsum:

A sulfate mineral composed of calcium sulfate dehydrate, with thechemical formula CaSO₄.2H₂O. In some embodiments, a disclosed fluidcomposition includes gypsum.

Insoluble or Weakly Soluble High pH Calcium-Formed Plant NutrientCompounds:

A phrase to describe compounds including calcium cyanamide, gypsum,calcium carbonate, calcium chloride or combinations thereof.

Nitrogen:

In its molecular form N₂, nitrogen makes up approximately 78% of theearth's atmosphere. Nitrogen is a component of all proteinaceous matterfound in living organisms, but only a few organisms (such asnitrogen-fixing bacteria) are able to directly capture atmosphericnitrogen and add it to the biosphere.

Proteinaceous matter, contained in dead and decaying organic matter andadditionally in the excreta of animals represents a vast potentialsource of nitrogen for growth of living organisms. However, inproteinaceous form, nitrogen is insoluble and unavailable to livingorganisms except through the action of decomposers, which releasenitrogen in the forms of gaseous NH₃ and leachable NH₄ ⁺, NO₂ ⁻, and NO₃⁻. These forms can be utilized by plants and allow nitrogen to reenterthe living biosphere. In some examples, the disclosed compositionsinclude nitrogen, such as in the form of nitrate.

Non-Nitrogen Material:

A material that does not contain nitrogen. In some examples, thenon-nitrogen material is a plant nutrient that does not containnitrogen. A non-nitrogen material can include phosphorous, potassium,iron, copper, zinc, manganese, boron, magnesium, molybdenum, sulfur,nickel and mixtures thereof.

Plant Nutrient:

A molecule that affects plant growth. A number of molecules have beendetermined to be essential to plant growth including carbon, oxygen,water, primary macronutrients including nitrogen (N), phosphorus (P),potassium (K), secondary macronutrients including calcium (Ca), sulphur(S), magnesium (Mg), macronutrient Silicon (Si), and micronutrients ortrace minerals (such as boron (B), chlorine (Cl), manganese (Mn), iron(Fe), zinc (Zn), copper (Cu), molybdenum (Mo), nickel (Ni), selenium(Se), and sodium (Na)). The macronutrients are consumed in largerquantities and are present in plant tissue in quantities from 0.2% to4.0% (on a dry matter weight basis). Micronutrients are present in planttissue in quantities measured in parts per million, ranging from 5 to200 ppm, or less than 0.02% dry weight.

Powdered-Activated Carbon (PAC):

Traditionally, active carbons are made in particulate form as powders orfine granules less than 1.0 mm in size with an average diameter between0.15 and 0.25 mm. Thus, they present a large surface to volume ratiowith a small diffusion distance. PAC is made up of crushed or groundcarbon particles, 95-100% of which will pass through a designated meshsieve. Granular activated carbon is defined as the activated carbonretained on a 50-mesh sieve (0.297 mm) and PAC material as finermaterial, while American Society for Testing and Materials (ASTM)classifies particle sizes corresponding to an 80-mesh sieve (0.177 mm)and smaller as PAC. PAC is not commonly used in a dedicated vessel, dueto the high head loss that would occur. PAC is generally added directlyto other process units, such as raw water intakes, rapid mix basins,clarifiers, and gravity filters.

Soil Microbes or Microorganisms.

Soil microorganisms, including, but not limited to, bacteria, fungi, andprotozoa, exist in large numbers in the soil as long as there is acarbon source for energy. A large number of bacteria in the soil exists,but because of their small size, they have a smaller biomass.Actinomycetes are a factor of 10 times smaller in number but are largerin size so they are similar in biomass to bacteria. Fungus populationnumbers are smaller but they dominate the soil biomass when the soil isnot disturbed. Bacteria, actinomycetes, and protozoa are hardy and cantolerate more soil disturbance than fungal populations so they dominatein tilled soils while fungal and nematode populations tend to dominatein untilled or no-till soils.

Soil organic matter (SOM) is composed of the “living” (microorganisms),the “dead” (fresh residues), and the “very dead” (humus) fractions. The“very dead” or humus is the long-term SOM fraction that is thousands ofyears old and is resistant to decomposition. Soil organic matter has twocomponents called the active (35%) and the passive (65%) SOM. Active SOMis composed of the “living” and “dead” fresh plant or animal materialwhich is food for microbes and is composed of easily digested sugars andproteins. The passive SOM is resistant to decomposition by microbes andis higher in lignin.

Microbes need regular supplies of active SOM in the soil to survive inthe soil. Long-term no-tilled soils have significantly greater levels ofmicrobes, more active carbon, more SOM, and more stored carbon thanconventional tilled soils. A majority of the microbes in the soil existunder starvation conditions and thus they tend to be in a dormant state,especially in tilled soils. Soil organic matter can be broken down intoits component parts. One hundred grams (g) or 100 pounds (lbs.) of deadplant material yields about 60-80 g (lbs.) of carbon dioxide, which isreleased into the atmosphere. The remaining 20-40 g (lbs.) of energy andnutrients is decomposed and turned into about 3-8 g (lbs.) ofmicroorganisms (the living), 3-8 g (lbs.) of non-humic compounds (thedead), and 10-30 g (lbs.) of humus (the very dead matter, resistant todecomposition).

Dead plant residues and plant nutrients become food for the microbes inthe soil. Soil organic matter (SOM) is basically all the organicsubstances (anything with carbon) in the soil, both living and dead. SOMincludes plants, blue green algae, microorganisms (bacteria, fungi,protozoa, nematodes, beetles, springtails, etc.) and the fresh anddecomposing organic matter from plants, animals, and microorganisms. Assoil microbes decompose organic residues, they slowly release nutrientsback into the soil for the winter cover crops or for the preceding crop.Higher temperatures and moisture increase the destruction of SOM byincreasing microbial populations in the soil. Organic residues with alow carbon to nitrogen (C:N) ratio (less than 20) are easily decomposedand nutrients are quickly released (4 to 8 weeks), while organic residuewith a high C:N ratio (greater than 20) decompose slowly and themicrobes will tie up soil nitrogen to decompose the residues. Protozoaand nematodes consume other microbes in the soil and release thenitrogen as ammonia, which becomes available to other microorganisms oris absorbed by plant roots.

Soil organic matter (SOM) is composed of mostly carbon but associatedwith the carbon is high amounts of nitrogen and sulfur from proteins,phosphorus, and potassium. Soils that are biologically active and havehigher amounts of active carbon recycle and release more nutrients forplant growth than soils that are biologically inactive and contain lessactive organic matter. Under no-till conditions, small amounts ofnutrients are released annually to provide nutrients slowly andefficiently to plant roots. However, with tillage, large amounts ofnutrients can be released since the SOM is consumed and destroyed by themicrobes. Since SOM levels are slow to build, the storage capacity fornutrients is decreased and excess nutrients released are often leachedto surface waters. SOM is a storehouse for many plant nutrients.

Urea or Carbamide:

An organic compound with the chemical formula CO(NH₂)₂. Urea serves arole in the metabolism of nitrogen-containing compounds by animals andis the main nitrogen-containing substance in the urine of mammals. It issolid, colorless, and highly soluble in water. Dissolved in water it isneither acidic nor alkaline. The body uses it in many processes, mostnotably nitrogen excretion. Urea is widely used in fertilizers as aconvenient source of nitrogen.

A temperature controlled oven study over 37 weekly water drenches ofeither urea only, 2 ratios of CaNCN/Urea or water only control throughloam soil columns with water catching pots demonstrated that urea, whichstayed below but near the ratios were soil amending and stayed in rootzones, suggesting desirable soil and plant root targets delivery traitsfor delivery in irrigation systems. The water control caused soilhardening and cracks, thus dropping through to the bottom from thebeginning.

Dry, water-soluble urea is a low cost, fast acting, and easilycalibrated soluble nitrogen form. However, urea is recognized to undergorapid hydrolysis, which may lead to ammonia gas release and/or lossesdue to nitrate leaching. Urea and excreta hydrolysis also contributelarge amounts of the greenhouse gas CO₂. In fact, urea and decomposedproteinaceous animal excreta containing urea are now considered soenvironmentally threatening that farmers using such fertilizers havealready been subject to fines and judgments for violation of clean waterlaws that regulate nitrates. It therefore would be desirable to providecompositions and methods that allow urea and animal excreta to beutilized as fertilizers without ammonia loss or rapid leaching ofnitrates.

There are two basic prior approaches to simultaneously makingurea-derived nitrogen available to plants for longer periods andreducing nitrate contamination. The first is to coated urea forreleasing urea slowly, called slow release. The second is to slow theconversion of urea to nitrate by soil microorganisms, either byinhibiting the action of urease or inhibiting nitrification, or both.

Urea dissolution control may be accomplished by coating urea withhydrophobic substances, such as sulfur, to produce slow releasegranules. U.S. Pat. No. 4,081,264 to Ali exemplifies this technology.Ali describes encapsulated slow release fertilizers prepared by coatinga fertilizer substrate (e.g., urea) with molten sulfur. Sulfur coatedurea particles are brittle so they are often coated with a plasticizingsubstance, such as bitumen, to increase their mechanical strength.Finally, another coating of an inorganic material, such as talc, may berequired to provide a free flowing material. While slow release granulescan extend nitrogen availability throughout the growing season andreduce nitrate leaching, they are too costly for general agriculturaluse, especially in light of their lower nitrogen content.

Urease inhibitors serve to slow the conversion of urea to ammonium ions.Such inhibitors include phosphoric triamides, such asN-(n-butyl)thiophosphoric triamide (NBPT) (see for example U.S. Pat. No.4,530,714). Phosphoric triamides however are difficult to handle andsusceptible to decomposition. Efficient incorporation of phosphorictriamides into granular urea-containing fertilizers may be accomplishedusing liquid amide solvents, but use of such solvents in the granulationprocess increases fertilizer costs.

Nitrification inhibitors, when combined with urea, ammonia, and ammoniumsalt fertilizers, also can serve to reduce nitrate leaching. Knownnitrification inhibitors include dicyandiamide (DCD) and N-Halaminecompounds. Dicyandiamide, which is made from calcium cyanamide, andforms in soil shortly after CaNCN delivery to moist soils also functionsas a nitrification inhibitor. It is however, short-lived in hot soils.

While calcium cyanamide is believed to function as both a urease andnitrification inhibitor, direct addition of calcium cyanamide to urea isdissuaded because the residual calcium form in commercial calciumcyanamide promotes ammonia volatilization, especially under wetconditions (Nianzu et al., Fertilizer Research, 41: 19-26, 1995).

What is needed therefore are compositions and methods that make itpossible to take advantage of calcium cyanamide's potential to mitigatenitrate leaching following application of urea. Furthermore, it would beadvantageous to provide compositions and methods that make it possibleto combine commercial calcium cyanamide directly with urea, even in wetconditions, and preserve the calcium form component of the calciumcyanamide and/or its water dissolution products. Disclosed is calciumcyanamide's carbon to activated or active carbon that more easily feedssoil microbes that thus will harbor nitrogen and other plant nutrients,that root hairs mine from them as they need it. The microbes continue tohold nitrogen, phosphorous and other nutrients for growing plant rootsto consume, preventing waste and loss to water environments.

Urea ammonium nitrate (UAN) is a solution of urea and ammonium nitratein water used as a fertilizer. The combination of urea and ammoniumnitrate has an extremely low critical relative humidity (18% at 30° C.)and is used in liquid fertilizers. The most commonly used grade of thesefertilizer solutions is UAN 32-0-0 (32% N) also known as UAN32 orUAN-32, which includes 50% urea, 25% ammonium nitrogen and 25% nitratenitrogen and 20% water. Other grades are UAN 28 (includes 40% ammoniumnitrate, 30% urea and 30% water), UAN 30 (includes 42% ammonium nitrate,33% urea and 30% water) and UAN 18. The solutions are corrosive towardsmild steel (up to 500 MPY on C1010 steel) and are therefore generallyequipped with a corrosion inhibitor to protect tanks, pipelines,nozzles, etc., or processed as herein newly disclosed to prevent suchcorrosive activity.

IV. Fluid Ionized Compositions

Disclosed herein are fluid ionized compositions, such as fluid calciumcyanamide fertilizer compositions. In some embodiments, a fluidcomposition includes a mixture of about 40 to 20 parts, such as 35 to 25parts, 30 to 20 parts, including 40 parts, 39 parts, 38 parts, 37 parts,36 parts, 35 parts, 34 parts, 33 parts, 32 parts, 31 parts, 30 parts, 29parts, 28 parts, 27 parts, 26 parts, 25 parts, 24 parts, 23 parts, 22parts, 21 parts, or 20 parts of dissolved acid or acid-formedapproximately neutral pH nitrogen plant nutrient compounds and about 1to about 10 parts, such as about 2 to 8 parts, about 3 to 7 parts, about1 to about 5 parts, including 1 part, 2 parts, 3 parts, 4 parts, or 5parts of a mixture of insoluble or weakly soluble high pH calcium-formedplant nutrient compounds. In some examples, the dissolved acid comprisesnitric acid, phosphoric acid, a weak carbonic acid or a combinationthereof and the acid-formed nitrogen plant nutrient compound are insolution and comprise ammonium nitrate, calcium nitrate, urea ammoniumnitrate, calcium ammonium nitrate, ammonium phosphate, high pH aqueousammonia or combinations thereof; and the insoluble or weakly solublehigh pH calcium-formed plant nutrient compounds are in solution andcomprise calcium cyanamide, gypsum, calcium carbonate, calcium chlorideor combinations thereof.

In some examples, the H₂O present in the fluid composition comprisesless than 14× the mass of the insoluble or weakly soluble high pHcalcium formed plant nutrient compounds in the mixture, such as about13×, about 12×, about 11×, about 10×, about 9×, about 8×, about 7×,including 13×, 12×, 11×, 10×, 9×, 8×, 7× the mass of the insoluble orweakly soluble high pH calcium formed plant nutrient compounds in themixture. In some embodiments, a composition including H₂O less than 14×the mass of the insoluble or weakly soluble high pH calcium formed plantnutrient compounds in the mixture is denoted as a concentrate. In someembodiments, the H₂O present in the fluid mixture comprises at least14×, such as about 14×, about 15×, about 16×, about 17×, about 18×,about 19×, about 20×, about 21×, about 22×, about 23×, about 24×, about25×, about 26×, about 27×, about 28×, about 29×, about 30×, including14×, 15×, 16×, 17×, 18×, 19×, 20×, 21×, 22×, 23×, 24×, 25×, 26×, 27×,28×, 29×, 30× the mass of the insoluble or weakly soluble high pHcalcium formed plant nutrient compounds in the mixture. In someexamples, a composition including H₂O at least 14× the mass of the massof the insoluble or weakly soluble high pH calcium formed plant nutrientcompounds in the mixture is prepared by diluting a concentrate.

In some examples, the insoluble or weakly soluble high pH calcium-formedplant nutrient compounds are in solution and ranges from about 0.1% byweight to less than about 30% by weight, more preferably from about 0.1%to less than about 20% by weight, even more preferably from about 0.1%to less than about 10% by weight, and typically between 5% to 10%, suchas about 7% and about 8%, including about 0.1%, about 0.5%, about 1%,about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%,about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%,about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about28%, about 29%, about 30%, by weight.

In some examples, a disclosed composition includes dissolved acid oracid-formed approximately neutral pH nitrogen plant nutrient compoundsincluding a urea ammonium nitrate (UAN), where the UAN solutioncomprises about 20% to about 40% urea, such as about 30% to about 35%urea, including 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%,31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40% of urea, about 30% toabout 55% ammonium nitrate, such as about 35% to about 50%, such asabout 40% to about 45% ammonium nitrate, including 35%, 36%, 37%, 38%,39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%,53%, 54%, 55% of ammonium nitrate with the residual as H₂O; and theinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds are in a solution comprising H₂O and comprise calciumcyanamide. In some embodiments, the H₂O present in the fluid mixturecomprises less than 14× the mass of calcium cyanamide, such as about13×, about 12×, about 11×, about 10×, about 9×, about 8×, about 7×,including 13×, 12×, 11×, 10×, 9×, 8×, 7× the mass of the calciumcyanamide in the mixture. In some examples, a composition including H₂Opresent in the fluid mixture less than 14× is denoted as a concentrate.In some embodiments, the H₂O present in the fluid mixture comprises atleast 14×, such as about 14×, about 15×, about 16×, about 17×, about18×, about 19×, about 20×, about 21×, about 22×, about 23×, about 24×,about 25×, about 26×, about 27×, about 28×, about 29×, about 30×,including 14×, 15×, 16×, 17×, 18×, 19×, 20×, 21×, 22×, 23×, 24×, 25×,26×, 27×, 28×, 29×, 30× the mass of the calcium cyanamide. In someexamples, a composition including H₂O at least 14× the mass of calciumcyanamide is prepared by diluting a concentrate.

In some examples, a disclosed composition includes calcium cyanamidefrom about 0.1% by weight to less than about 30% by weight, morepreferably from about 0.1% to less than about 20% by weight, even morepreferably from about 0.1% to less than about 10% by weight, andtypically between 5% to 10%, such as about 7% and about 8%, includingabout 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%,about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about25%, about 26%, about 27%, about 28%, about 29%, about 30%, by weight.

In some examples, a disclosed composition further includes excreta, suchas liquidized excreta (e.g., an aqueous manure slurry). In someexamples, the excreta is animal excreta, such as dairy or swine excreta.

In some embodiments, the disclosed composition includes from about 0.01percent calcium cyanamide to about 99.99 percent UAN solution and fromabout 0.1 percent to about 99.9 percent fluid excreta.

In some embodiments, the disclosed composition includes about 25 percentcalcium cyanamide, 25 percent to about 50 percent UAN solution and fromabout 50 percent to about 25 percent excreta.

It is possible to include other plant fertilizing materials, nutrientsand soil amendments in embodiments of the compositions of the presentdisclosure. Other plant fertilizers, nutrients and soil amendmentsinclude, but are not limited to, phosphorous, potassium, iron, copper,zinc, manganese, sulfur, boron, magnesium, molybdenum, and mixturesthereof. A more exhaustive list of plant nutrients, includingmicronutrients, is found in the official publication of the Associationof American Plant Food Control Officials (AAPFCO), volume 53, 2000 orlater, which is incorporated herein by reference.

In some examples, a disclosed composition includes at least onenon-nitrogen material to the mixture, such as a plant nutrient. In someexamples, the non-nitrogen material includes phosphorous, potassium,iron, copper, zinc, manganese, boron, magnesium, molybdenum, sulfur,nickel, and mixtures thereof.

In some examples, a disclosed composition includes an electrolyticsuspension agent, such as an ionized metal element, such as silicon,iron, aluminum, carbon or a combination thereof.

In some examples, the approximately neutral pH nitrogen plant nutrientcompound mixture includes a pH of about 7.4 and about 8, such as about7.6 and about 7.9, such as about 7.8 and 7.9. such as about 7.4, about7.5, about 7.6, about 7.7, about 7.8, about 7.9 or about 8.

In some examples, a disclosed composition includes particles of with anabout 60 to about 240 mesh pass through, such as about 80 to about 200mesh pass through, such about 60, about 80, about 100, about 120, about180, about 200 mesh pass through.

Compositions of the present disclosure can be prepared, transported,sold and stored in containers. Prior disclosures required that calciumcyanamide fertilizers be prepared and maintained in the absence ofaeration to prevent soluble calcium ions forming inactive CaCO₃. Inparticular, aeration of the mixture was inhibited, for example, byforming the mixture in a container, where the container also held a gas,such as nitrogen, argon, ammonia, acetylene, and mixtures thereof, thatserves to inhibit gas exchange between the container and the atmosphere.It has been surprisingly determined herein that the disclosedcompositions do not need be prepared or maintained in sealed containers,and in fact, can be exposed to air, or other gas, including carbondioxide (which is accelerated by open-air agitation) without causingsoluble calcium ions to form inactive CaCO₃.

V. Methods of Making a Fluid Ionized Composition

Methods of making a disclosed fluid ionized composition are provided. Insome examples, a method of making a fluid composition includes combininga mixture of about 40 to 20 parts, such as 35 to 25 parts, 30 to 20parts, including 40 parts, 39 parts, 38 parts, 37 parts, 36 parts, 35parts, 34 parts, 33 parts, 32 parts, 31 parts, 30 parts, 29 parts, 28parts, 27 parts, 26 parts, 25 parts, 24 parts, 23 parts, 22 parts, 21parts, or 20 parts of dissolved acid or acid-formed approximatelyneutral pH nitrogen plant nutrient compounds and about 1 to about 10parts, such as about 2 to 8 parts, about 3 to 7 parts, about 1 to about5 parts, including 1 part, 2 parts, 3 parts, 4 parts, or 5 parts of amixture of insoluble or weakly soluble high pH calcium-formed plantnutrient compounds, thereby forming a fluid composition. In someexamples, the dissolved acid comprises nitric acid, phosphoric acid, aweak carbonic acid or a combination thereof and the acid-formed nitrogenplant nutrient compound comprises ammonium nitrate, calcium nitrate,urea ammonium nitrate, calcium ammonium nitrate, ammonium phosphate,high pH aqueous ammonia or combinations thereof; and the insoluble orweakly soluble high pH calcium-formed plant nutrient compounds comprisecalcium cyanamide, gypsum, calcium carbonate, calcium chloride orcombinations thereof.

In some examples, the approximately neutral pH nitrogen plant nutrientcompound mixture has a pH of about 7.4 and about 8, such as about 7.6and about 7.9, such as about 7.8 and 7.9. such as about 7.4, about 7.5,about 7.6, about 7.7, about 7.8, about 7.9 or about 8.

In some examples, H₂O is added to the mixture so that the resultingfluid composition comprises less than 14× the mass of the insoluble orweakly soluble high pH calcium formed plant nutrient compounds in themixture, such as about 13×, about 12×, about 11×, about 10×, about 9×,about 8×, about 7×, including 13×, 12×, 11×, 10×, 9×, 8×, 7× the mass ofthe insoluble or weakly soluble high pH calcium formed plant nutrientcompounds in the mixture. In some examples, a concentrate of a disclosedcomposition is prepared by including H₂O less than 14× the mass of theinsoluble or weakly soluble high pH calcium formed plant nutrientcompounds in the mixture.

In some examples, H₂O is added to the mixture so that the resultingfluid composition comprises at least 14×, such as about 14×, about 15×,about 16×, about 17×, about 18×, about 19×, about 20×, about 21×, about22×, about 23×, about 24×, about 25×, about 26×, about 27×, about 28×,about 29×, about 30×, including 14×, 15×, 16×, 17×, 18×, 19×, 20×, 21×,22×, 23×, 24×, 25×, 26×, 27×, 28×, 29×, 30× the mass of the insoluble orweakly soluble high pH calcium formed plant nutrient compounds in themixture. In some examples, a composition including H₂O at least 14× themass of the mass of the insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds in the mixture is prepared byadding the desired amount of H₂O to a prepared concentrate.

In some examples, fluid compositions are prepared by adding theinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds to a solution, ranging from about 0.1% by weight to less thanabout 30% by weight, more preferably from about 0.1% to less than about20% by weight, even more preferably from about 0.1% to less than about10% by weight, and typically between 5% to 10%, such as about 7% andabout 8%, including about 0.1%, about 0.5%, about 1%, about 2%, about3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%,about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%,about 30%, by weight.

In some examples, a disclosed composition which includes urea ammoniumnitrate (UAN) is prepared by combining a UAN solution comprising about20% to about 40% urea, such as about 30% to about 35% urea, including20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%,34%, 35%, 36%, 37%, 38%, 39%, 40% of urea, about 30% to about 55%ammonium nitrate, such as about 35% to about 50%, such as about 40% toabout 45% ammonium nitrate, including 35%, 36%, 37%, 38%, 39%, 40%, 41%,42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55% ofammonium nitrate with H₂O and calcium cyanamide. In some examples, thefluid composition is prepared so that H₂O is less than 14× the mass ofcalcium cyanamide, such as about 13×, about 12×, about 11×, about 10×,about 9×, about 8×, about 7×, including 13×, 12×, 11×, 10×, 9×, 8×, 7×the mass of the calcium cyanamide in the composition. In some examples,a concentrate of a fluid composition including calcium cyanamide isprepared by adding H₂O at a volume so that it is less than 14× the massof calcium cyanamide.

In some examples, the H₂O is added to a fluid mixture including calciumcyanamide so that the H₂O is at least 14× the mass of calcium cyanamide,such as about 14×, about 15×, about 16×, about 17×, about 18×, about19×, about 20×, about 21×, about 22×, about 23×, about 24×, about 25×,about 26×, about 27×, about 28×, about 29×, about 30×, including 14×,15×, 16×, 17×, 18×, 19×, 20×, 21×, 22×, 23×, 24×, 25×, 26×, 27×, 28×,29×, or 30× the mass of calcium cyanamide. In some examples, acomposition including H₂O at least 14× the mass of calcium cyanamide isprepared by diluting a concentrate.

In some examples, a disclosed composition is prepared by adding calciumcyanamide from about 0.1% by weight to less than about 30% by weight,more preferably from about 0.1% to less than about 20% by weight, evenmore preferably from about 0.1% to less than about 10% by weight, andtypically between 5% to 10%, such as about 7% and about 8%, includingabout 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%,about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about25%, about 26%, about 27%, about 28%, about 29%, about 30%, by weight toa solution including H₂O and UAN.

In some examples, excreta, such as liquidized excreta (including, butnot limited to dairy excreta), is combined with a mixture comprisingabout 40 to 20 parts of dissolved acid or acid-formed approximatelyneutral pH nitrogen plant nutrient compounds to about 1 to about 5 partsof a mixture of insoluble or weakly soluble high pH calcium-formed plantnutrient compounds, where the dissolved acid includes nitric acid,phosphoric acid, a weak carbonic acid or a combination thereof and theacid-formed nitrogen plant nutrient compound are in solution andcomprise ammonium nitrate, calcium nitrate, urea ammonium nitrate,calcium ammonium nitrate, ammonium phosphate, high pH aqueous ammonia orcombinations thereof and the insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds are in solution and comprisecalcium cyanamide, gypsum, calcium carbonate, calcium chloride orcombinations thereof, thereby forming a fluid composition.

In some examples, other plant fertilizing materials, nutrients and soilamendments are combined with a disclosed fluid composition. Other plantfertilizers, nutrients and soil amendments include, but are not limitedto, phosphorous, potassium, iron, copper, zinc, manganese, sulfur,boron, magnesium, molybdenum, and mixtures thereof.

In some examples, at least one non-nitrogen material, such as a plantnutrient, is added to the fluid mixture. In some examples, non-nitrogenmaterials, such as phosphorous, potassium, iron, copper, zinc,manganese, boron, magnesium, molybdenum, sulfur, nickel, or mixturesthereof are added to the mixture.

In some examples, an electrolytic suspension agent is added to themixture. Exemplary electrolytic suspension agents include, but are notlimited to, ionized metal elements, such as silicon, iron, aluminum,carbon or a combination thereof.

In some examples, a disclosed composition is prepared to yield particleswith an about 60 to about 240 mesh pass through size, such as about 80to about 200 mesh pass through, such about 60, about 80 about 100, about120, about 180, about 200 mesh pass through size.

In some examples of the method of making, the combining is performed inthe presence of a circulation process. It is contemplated that anycirculation process known to one of skill in the art may be used toprepare the fluid compositions. In some examples, a venturi by-passsystem or other like intensive blending system is used to prepare adisclosed fluid composition.

The disclosed methods can be performed in an opened vessel or a closedvessel. The efficiency of the method is not dependent upon the absenceof atmospheric gases, such as CO₂. Further, no additives or heat arerequired to maintain the fluid state of the compositions. In someexamples, the method is performed in an opened container. In someexamples, the method is performed in an unsealed container. In someexamples, the method is performed in the presence of atmospheric CO₂. Insome examples, the method of making is performed in an opened container,an unsealed container, and/or in the presence of atmospheric CO₂. Whilethe method may be performed in a closed container, it is not required.

In some examples, the method of making further includes dehydrating thefertilizer composition to form a solid. By forming the disclosed liquidcompositions, such as fluid compositions comprising calcium cyanamide,and dehydrating them, it is possible to provide solids that contain theinitial dissolution and hydrolysis products of calcium cyanamide in areadily dissolvable, calibrateable, and stable form.

Processes for dehydration of liquid compositions to provide solidmaterials are well known in the chemical and fertilizer arts. In itssimplest form, water from an aqueous composition can simply be allowedto evaporate. It is possible to accelerate the evaporation process byusing a vacuum, by bubbling a gas, such as an inert gas, through thecomposition, or by allowing the composition to evaporate under aprotective blanket of inert gas, for example argon. Heat can also beemployed to stimulate evaporation. Freeze-drying of aqueous compositionsis another alternative. During freeze drying, a vacuum is used tosublime water from the frozen liquid composition. Dehydration equipmentis available from MCD Technologies (Tacoma, Wash.).

VI. Methods of Use

Disclosed herein are methods of using the provided fluid ionizedcompositions. These uses include agricultural uses, such as fertilizingand/or soil amending compositions (such as increasing soil base ofbeneficial microbes) as well as for disinfecting and controlling odorsof certain materials, including fertilizing and/or waste materials, suchas, without limitation, human waste effluents, livestock manure andwaste effluents, garbage, oils, plant materials, such as vegetablewaste, and paper processing materials. While not limiting the presentdisclosure to a particular theory of operation, it is believed that thedisclosed synergistic compositions in use, derive their efficacy inlarge part from a stabilization of the bioactive acid cyanamide ion andsoluble calcium such as provided by calcium cyanamide and gypsumCaSO₄.2H₂O. In addition, the efficacy of the synergistic compositionsmay derive from the discovery of the ability of these compositions toenhance soil permeability and allow percolation of the bioactivecyanamide ion and soluble calcium ions into plants at or above groundlevel and deep into the soil for root uptake.

Using the methods described herein as fertilizing and soil amendingcompositions, or as odor-controlling and disinfecting compositions,typically comprises (1) forming the compositions, and (2) applying thecompositions to various materials and/or locations, such as odiferousmaterials, particularly human and animal wastes and fluids,slaughterhouse wastes, or agricultural plots. The compositions areformed as described above. Once formed, the compositions can be appliedto odiferous materials and/or agricultural plots by any suitable method,including by hand or using conventional spraying or irrigationtechniques. In some examples, the disclosed compositions are applied asaqueous dispersions, including both suspensions and filtered solutions.For example, a concentrate composition may be diluted to a desiredconcentration by adding an additional solvent, such as H₂O, mixed,decanted and/or filtered as desired, and thereafter applied toagricultural plots, such as by using conventional spraying andirrigation injection devices. The disclosed compositions provide adistinct advantage in that spraying devices can conveniently be usedwithout the heretofore ubiquitous clogging problems associated withusing the conventional, substantially large particles of calciumcyanamide or those which required aeration inhibition.

In particular, methods of treating excreta, methods of enhancing plantgrowth and methods of digesting insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds are disclosed.

i. Methods of Treating Excreta

In some examples, methods of treating excreta can include adding aneffective amount of a disclosed fluid composition such as thosedescribed in detail in Section IV to excreta, such as animal excreta. Insome examples, an effective amount is one in which the H₂O present inthe fluid composition comprises at least 14× the mass of the insolubleor weakly soluble high pH calcium formed plant nutrient compounds. Thedisclosed methods can be used to treat excreta, such as animal excreta,in various forms including liquidized manure. In some examples, theexcreta is dairy, swine or chicken.

In some examples, the method further includes adding at least onenon-nitrogen material to the mixture, such as a plant nutrient. In someembodiments, the non-nitrogen material is selected from the groupconsisting of phosphorous, potassium, iron, copper, zinc, manganese,boron, magnesium, molybdenum, sulfur, nickel, and mixtures thereof.

In some examples, the method further includes adding an electrolyticsuspension agent to the mixture, such as an ionized metal element, suchas silicon, iron, aluminum, carbon or a combination thereof.

In some examples, the approximately neutral pH nitrogen plant nutrientcompound mixture has a pH of about 7.8 and 7.9.

In some examples, the fluid composition comprises particles of with anabout 60 to about 100 mesh pass through screen size, such as about 80 toabout 100 mesh pass through screen size.

In some examples, the method of treating excreta further includesapplying the mixture to plants, soils or mediums through an irrigationsystem, for example a fertigation/nitrigation system. In some examples,the method of treating excreta includes applying a disclosed compositionto the soils, plants or mediums including excreta by spraying.

In some examples, the method of treating excreta includes treatingmunicipal effluent waste, for example in treatment facilities.

ii. Methods of Enhancing Plant Growth

Methods of enhancing plant growth are disclosed. In some examples, amethod of enhancing plant growth includes applying an effective amountof a disclosed fluid composition in which the H₂O present in the fluidcomposition comprises at least 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds to soil priorto, during and/or after planting, thereby enhancing plant growth.

In some embodiments, applying an effective amount comprises applying thecomposition to plants, soils or mediums through an irrigation system,for example a fertigation/nitrigation or drip system. In some examples,the method of enhancing plant growth comprises applying an effectiveamount of a disclosed composition to the soils, plants or mediumsincluding excreta by spraying.

In some embodiments, methods of enhancing plant growth comprise applyingquantum harmonic resonance for molecular and electron spin for adextrorotary bias to increase compatibility with biological systems(QHR) or mechanical method of imparting a heavy/complete dextrorotarybias to molecular and electron spin to increase compatibility withbiological systems (MDB) to the disclosed compositions in vessels of thedisclosed compositions. Thus, methods of modulating the electron spin ofelements within a fluid composition are also disclosed. In someembodiments, methods of enhancing plant growth comprise exposing theplants to sound, such as audible, low frequency sound of less than 4000Hertz, prior to, during, and/or following treatment with one or more ofthe disclosed fluid compositions. For example, the frequency of thesound is selected to enhance plant leaf pore opening.

iii. Methods of Digesting Insoluble or Weakly Soluble High pHCalcium-Formed Plant Nutrient Compounds

Methods of digesting insoluble or weakly soluble high pH calcium-formedplant nutrients to form ionized calcium compounds are disclosed. In someembodiments, a method of digesting insoluble or weakly soluble high pHcalcium-formed plant nutrient compounds to form ionized calciumcompounds includes combining a mixture of about 40 to about 20 parts ofdissolved acid or acid-formed approximately neutral pH nitrogen plantnutrient compounds to about 1 to about 5 parts of a mixture of insolubleor weakly soluble high pH calcium-formed plant nutrient compounds, wherethe dissolved acid comprising nitric acid, phosphoric acid, a weakcarbonic acid or a combination thereof and the acid-formed nitrogenplant nutrient compound are in solution and comprise ammonium nitrate,calcium nitrate, urea ammonium nitrate, calcium ammonium nitrate,ammonium phosphate, high pH aqueous ammonia or combinations thereof andhydrolyze the insoluble or weakly soluble high pH calcium-formed plantnutrient compounds in solution which comprise calcium cyanamide, gypsum,calcium carbonate, calcium chloride or combinations thereof, therebyforming ionized calcium compounds and insoluble carbon.

In some examples of the method of digesting, the mixture of insoluble orweakly soluble high pH calcium-formed plant nutrient compounds includescalcium cyanamide.

In some examples of the method of digesting, the combining is performedin the presence of a circulation process, such as a venturi by-passsystem or other like intensive blending system.

In some embodiments, the method further comprises applying sound.

iv. Methods of Digesting Proteinaceous Matter

Methods of digesting proteinaceous matter are disclosed. In someembodiments, a method of digesting proteinaceous matter is a method foralkaline digestion of proteinaceous matter by using ammonia in water. Insome examples, proteinaceous matter is a plant, a plant part or a plantseed. In some examples, the method includes forming ammonia byhydrolyzing urea in water. For instance, calcium cyanamide is used tohydrolyze urea in water. In some examples, the method includes usingcalcium cyanamide comprising calcium to hydrolyze urea in water. In someexamples, the calcium within the calcium cyanamide is employed tohydrolyze the urea in urea ammonium nitrate.

In some examples of the method of digesting, the combining is performedin the presence of a circulation process, such as a venturi MDB by-passcirculation system or the QHR resonance system or other like intensiveblending systems.

Urea is produced by compressing CO₂ with ammonia (NH₃). Fluid UreaAmmonium Nitrate UAN comprises water in percentages from 30 to 20% as tothe concentration of urea and ammonium nitrate dissolved in water tocomprise 28% or 32% nitrogen.

In the present disclosure calcium cyanamide is hydrolyzed in a vessel offluid UAN comprising water. That creates soluble ionic calcium, whichaggressively hydrolyses urea in water back to its original components ofammonia and CO₂. Typically and with this process UAN can have ammonia.

This disclosure also describes ammonium being hydrolyzed, disassociatedor separated away from its original component nitric acid, which canfurther digest calcium from calcium cyanamide's other calcium compoundsand metal nutrients compounds creating other soluble ionic nutrientforms. Importantly, this includes digesting calcium canamide's freegraphite carbon to very active carbon, easily absorbed and digested bysoil microbes that depend on their energy coming from carbon, when themixture compositions are applied to the soil for farming.

This disclosure further discloses a method of pumping through a MDBby-pass circulation system that pounds all the disclosed compoundstogether in a blending process. This particle pounding mechanism helpsdigest the particles in all of calcium cyanamide's components or anyother nutrients compounds added to the mixture. This creates solutiongrade sprayable fluid ionic calcium cyanamide that contains ammonia.

v. Methods of Digesting Free Carbon into Solution Grade to Enhance SoilMicrobes' Carbon Consumption

Methods of digesting free carbon into solution grade to enhance soilmicrobes' carbon consumption are disclosed. In some embodiments, amethod of digesting free carbon into solution grade to enhance soilmicrobes' carbon consumption includes using resonance QHR) or mechanicalblending systems (HDB) to create activated carbon with more surface areafor even more access to microbes. In some examples, the method includesapplying the disclosed compositions to soil that has been tilled. Inother examples, the method includes applying the disclosed compositionsto soil that has not been recently tilled, such as within the past 12months, 24 months, 36 months or more. It is contemplated that the methodincludes applying one or more of the disclosed compositions to the soilby any means known to one of ordinary skill in the art, including thosementioned within this disclosure.

The foregoing may be better illustrated by the following example. Otheraspects and advantages of the present invention are illustrated in theexample which is provided solely for purposes of illustration. The scopeof the present disclosure should not be limited to those featuresdescribed in this example.

EXAMPLE

This example describes various studies characterizing the disclosedfluid compositions.

Table 1 illustrates the carbon suspension levels in static jars overtime. This data was created from static clear jar mixtures of CaNCN inUAN 32 and CaNCN in urea and water and grading them as to visible levelsof carbon from CaNCN over time. FIG. 1 compares carbon black colorlevels in jars. Here, the UAN with less water was a more dense solutionthan urea in water, thus the former holds up the black CaNCN particleslonger.

TABLE 1 CaNCN in BLACK CaNCN in UREA MINUTES UAN 32 WATER 0 100% 100% 5100% 80% 15 100% 20% 30 100% 10% 1 Hr 50% 5% 2 Hrs 20% 2% 3 Hrs 15% 0% 4Hrs 5% 0%

Table 2 displays the color density of black carbon from light throughjars at various time intervals. Table 2 data was created from staticclear jar mixtures of CaNCN in UAN 32 and CaNCN in urea and water andgrading them as to visible levels of carbon from CaNCN over time, whileshining a bright light into them. The less color, the finer the coloredparticles are. FIG. 2 graphically compares the fineness of digestedparticles. Here it appears that the alkaline aqua ammonia aided acidformed compounds in UAN are digesting the black carbon CaNCN particles.

TABLE 2 BLACK CaNCN in CaNCN in MINUTES 100% UAN 32 25% UAN 75% AquaAmm.  0 100% 100%  5 100% 90% 15 70% 20% 30 50% 20% SHAKE 100% 100%  1Hrs 80% 20% SHAKE 100% 100%  1 Hrs 80% 50%  2 Hrs 10% 5%

Table 3 displays particle sizes from static jar tests after passingthrough screen sizes. Table 3/FIG. 3 data was created from static clearjar mixtures of CaNCN in water, UAN 32, AN 20, CAN 17 and suspensionagent in water judging them as to passage through 2 grades of finerscreens than used in farm spraying practices. Additionally included wasa screening judgment made of CaNCN in UAN from a commercial venturi MDBsystem. Intended was to comparatively display differences betweendiluents and the overall benefit from venturi MDB processing.

TABLE 3 CaNCN PASS PASS IN FLUIDS 100 MESH 200 MESH WATER 20% 5% UAN 32100% 95% AN 20 100% 90% CAN 17 100% 95% AGENT 100% 100% VENTURI 100%100%

Table 4 illustrates percentage of cyanamide hydrolysis in the presenceand absence of UAN by adding either 7 grams of CaNCN to 100 ml DI wateror 7 grams of CaNCN to 95 ml DI water and 5 ml UAN 32. This is anaddition of 5% UAN containing 20% water to a 14× water mixture to CaNCN(essentially maintaining a 7% solution) increase cyanamide yield by 25%in 15 minutes. UAN was observed to break apart the black solids tocreate a black solution within this short period of time. Such effectwas not observed in the water only solution. This result indicates thatif the CaNCN is 14× proportionately in UAN's 20% water inside UAN andthus exposed to 118× more UAN, the apparent aggressive hydrolyzation ofUAN seen here can increase these results to attain full theoreticalhydrolyzation within this 15 minute time limitation.

TABLE 4 7 gm CaNCN/100 ml Di 7 gm CaNCN/95 ml Di Water Water and 5 mlUAN 32 % of Cy Hydrolysis 40% 50% 15 min.

Table 5 demonstrates the importance of particle hardness and sizerelated to speed and completion of CaNCN hydrolysis over time. Table 5data was created by lab titrations to net cyanamide yields from hardenedCaNCN granules and microchips of CaNCN used in the present disclosure.This differentiates CaNCN microchip powder (0.0-0.1 mm powder) (18 to200 mesh screen size) from commercially hardened and enlarged granules(1.7-3.5 mm) (12 to 5.5 mesh screen size).

TABLE 5 Hardened CY YIELDS Granules Microchips DAYS CaNCN CaNCN 1 0.2750.475 3 0.375 0.500 5 0.375 0.500 8 0.400 0.550

Table 6 and FIG. 6 illustrate the field corn yield and sugar increasesfrom fluid 0.5% CaNCN Stabilized UAN 32 over standard fluid UAN 32, inArise Research and Discovery Station, Martinsville, Ill., triplereplicated field corn nitrogen fertilized studies. These are averagesover 60-120-180 lbs. Nitrogen/acre. Three field corn studies thatincluded yields and chlorophyll related plant sap sugar brix studieswere performed.

TABLE 6 SUGAR YIELD/SUGAR YIELD BRIX PERCENTS INCREASE INCREASE 0.25%CaNCN/UAN 32 13% 33%

Table 7 and FIG. 7 display the time degradation effect of CaNCN in fluiddairy manure. This data was generated from extensive laboratory studiesthat graded disappearance and appearance of negative and positivesensations and visuals from CaNCN treated fluid dairy excreta.

The operative is the digestion of feces and thus the source of stinkodor and harborant food for human harmful organisms. Not shown is thatCaNCN increases beneficial organisms, included in the term coliform, ofwhich is included human harmful coliform. Laboratory analysis showed anincrease in beneficial “coliform” while human harmful e-coli coliformwas un-detectable. Exposure of CaNCN was over a 5 day period.

TABLE 7 0.2% CaNCN In Fluid Manures NP Time Stink Odor e-Coli LeachableFibers Solids  5 Min 0% 100% 100% 100% 24 Hrs 0% 5% 80% 90%  2 days 0%4% 60% 80%  3 days 0% 3% 40% 60%  4 days 0% 2% 20% 50%  5 days 0% 0% 0%10%

Table 8 and FIG. 8 show synergistic fertilizer ancillary reduced plantcompeting weed pressure between pre-plant strawberry fertilizing with1.) 750 lbs. hardened granules CaNCN/acre on 5 weed species, 2.)decanted aliquot from making 82 lbs. CaNCN/acre together with 190 lbs.of urea/acre in water on 7 weed species, 3.) disclosed fertilizedcompositions from making 8 lbs./acre CaNCN together with 289 lbs. UAN insolution/acre on 7 weed species. The 8 lbs. was a dramatic, unexpected9× and 94× reduction of CaNCN use and 8 lbs./289 lbs. was 100% alkalineweed seed tissue digestion versus less than 100% from 94× more CaNCN.This was a visually clear demonstration of CaNCN's synergisticcontribution to making soluble and some weakly soluble common fertilizercompounds into disclosed soluble, plant absorbable, ionic nutrientssolution (FIG. 8 far right 3^(rd) bar displays this effect).

TABLE 8 FERTILIZER WEEDS NOT RATES EMERGED 750 lbs CaNCN/Acre Granular96%  82 lbs CaNCN/Acre 190 lbs UREA (Aliquot) 95%  8 lbs CaNCN/Acre 289lbs UAN (Solution) 100%

At about 1 part of CaNCN fertilizer to about 40 to about 100 parts ofcommon fluid nitrogen fertilizers, this record of visuals shown in FIG.8 displays the disclosed operative of improved nutrient efficiencyexpressed by fertilizer ancillary effects. As seen in FIG. 8, theeffects are from the common fluid fertilizers, ionized to electrolytesolutions by CaNCN, not from CaNCN itself. This visually displays thesynergistic ratio between CaNCN and common fertilizers, disclosed in thetables and figures.

One of the most practical and surprising operative of this disclosure isthat the effects were achieved at practical rates of nitrogen per acre.The CaNCN/UAN rates were 106 and 94 lbs. of nitrogen/acre whereas theCaNCN rate/acre was at 180 lbs. of nitrogen/acre, which is consideredexcessive for environmental protection purpose. A CaNCN/UAN rate of 50lbs./acre attained a 90% emergence reduction of nut grass, which evenozone suspect gaseous methyl bromide gas cannot attain at 350 lbs. peracre.

The cost of the base fertilizers added to CaNCN is zero, because theyare assessed against typical nitrogen nutrient feeding by commonfertilizer at standard rates/acre.

The disclosed method of soil pre-plant placement was concentrated atabout 4 inches deep, where new, newly planted, strawberry plant rootsare to reside two weeks later. Over the following 9 months of thestrawberry season, standard UAN solution is typically post-plant dripnitrigated at non-plant-harmful rates/acre. 1 lb./acre CaNCN in UANstabilizes that UAN. Such CaNCN/UAN drips induced ancillary effects ofuniform blossoming and fruit pickings, expected from carbon/nitrogen andammonium N forms and electrolyte solutions created by the disclosedsolutions. Such effects at 1 lb. CaNCN/acre in UAN, pre-plant sprayedonto cultivated soil are confirmed by disclosed FIGS. 6, 10, and 11 cornstudies.

Additionally, the disclosed effect on weed emergence calls attention tothe published effect of Alkaline Tissue Digestion (Alkaline Hydrolysis);U.S. patented Christmas day 1888, Amos Herbert Hobson, Middlesex,England, 394,982, where the disclosed tissue is weed seeds. Weed seedemergence made underground effects visible. Invisible microscopic plantroot antagonists are likely similarly affected. The latter'sreproduction is pH sensitive. The disclosed, no-heat, cultural practiceeffects were recorded by Hartmann as a temporary high soil pH shift.

The disclosed 38× and 125×>“8 lbs./acre CaNCN” (about 2.5%) clearlydemonstrates that the disclosed dynamic alkaline tissue digesting effectis from 0.25%-2.5% CaNCN stabilized UAN fertilizing, not from CaNCNfertilizing. The likely operative for the disclosed visual effect ofalkaline weed seed tissue digestion is the last in a sequence of UANphases from CaNCN particle digesting to the disclosed fluid equilibriumcompositions.

CaNCN in water reaches 12.2 pH. UAN nitric acid alkaline metalsdigestion first attains 9.5 pH. Continuing Ca++ alkaline acid metalsdigestion attains final pH 8.5. Ca++ urea polymer digestion to NH₃ gascan attain pH 14. Its dilution in water to 24% NH₄ (NH₄OH) equilibriumis typically 12 to 13 pH.

Stabilized NH₄ nitrogen is naturally preferred by plants.Non-CaNCN-stabilized NH₄ transforms to leachable NO₃ N which plantscannot use, that robs plants of energy because they lose energy byconverting it back to plant useable NH₄. This statement is consistentwith disclosed 10× less 0.25% CaNCN stabilized UAN increasing ear leafnitrogen, 29% more yield and 33% more sugar energy, disclosed in Tablesand FIGS. 6 and 11.

Table 9 and FIG. 9 display the visual responses to freezing overnighttemperature of jarred dilute 0.5% CaNCN in UAN 32. Table 9 data wasdeveloped from observations of static jars of the disclosed solutions inwinter overnight and freezer conditions and confirmed by mid-winterMissouri overnight observations. Clearly it displayed that CaNCN in UAN,even at lowest dose, prevents freezing of commercial UAN 32 down to zero° F. One such observation was at 5 degrees below zero.

TABLE 9 0 Deg. F. FREEZING UAN CaNCN Stabilized PERCENTS 32 UAN 32 JarCrystals 90% 0% Ice Slush Gauze Catch 100% 0%

Table 10 and FIG. 10 display field corn yield increases from CaNCNinside UAN at two levels of 0.25% and 0.5%. This information suggeststhat 0.25% is enough to create stabilized nitrogen in 99.75% UAN.

The principal of this stabilizing technology is for CaNCN to induceearly release of its diluents' N nutrients for early baby plant rootsfeeding so the nutrients are plant captured for succeeding plantmaturity phases through harvest, instead of being lost to early in-soilleaching.

Stabilized indicates succeeding in-season reproductive, resistantgrowth. This phenomenon is of record for CaNCN. CaNCN at 1 lb./acreinside 100 lbs. of UAN nitrogen (N)/acre suggests synergistic actionbetween UAN and hydrolyzed CaNCN. This means that all of UAN can expressunique reproductive and ancillary fertilizer responses.

TABLE 10 CaNCN BUSHELS PERCENTS INCREASE 0.25% CaNCN/UAN 7%  0.5%CaNCN/UAN 7%

Table 11 and FIG. 11 display the improved nitrogen content in the earleaves of field corn from 0.5% CaNCN inside fluid UAN. This evaluationis standard in determining the ratio and destinations of soil appliednitrogen.

Corn kernel yields from corn ears are the objective of applied nitrogen.The ear leaf sap is likely to indicate what degree of applied nitrogenhas reached the corn ears. CaNCN inside UAN was recorded as not onlyinfluencing reproductive corn growth, but also increasing chlorophyllrelated to recovered increased sugar brix in growing corn stock andleaves' sap, likely to be expressed in corn kernels, “intuitivelypreferred by animals.”

This has also been recorded as making 2.8× more food from corn and 150more gallons of biofuel/acre, all on today's corn acres. At $2.50/gallonof gas this can generate 1/2 $Trillion to U.S. treasuries and jobseconomy.

TABLE 11 YIELD/LEAF N YIELD EAR LEAF N PERCENTS INCREASE INCREASE 0.5%CaNCN/UREA 2% 11%

FIG. 12 illustrates the U.S. nitrogen fertilizer market shares per annumfor both dry and fluid nitrogen fertilizers. Putting CaNCN usage topractice as in these disclosures to 50% U.S. market share nitrogensolutions is most likely to reach most of the nation's watersheds forcleaner waters and air and farm fertilizing practice benefits inmultiples over any other means.

FIG. 13 illustrates that carbon that feeds soil microbes that feed plantroot growth, can be a constant companion with the ionic plant nutrientsdisclosed herein. Each of the columns depicts jars of insoluble CalciumCyanamide (CaNCN) in UAN for 25 days. The left hand column, with twolevels of gray settlement, resulted from hand shaking 5% dry CaNCN in ajar of UAN; the middle column, with no settlement, resulted from dumpingpre-venturi blended 5% CaNCN in UAN into an empty jar; and the righthand column depicted where carbon from CaNCN statically floats in a jarof UAN from slowly pouring Pre-venturi blended 5% CaNCN at a 1 to 10ratio into a jar of UAN. This opportunity to visually see the status ofcarbon in saturated UAN indicates fluid ionized compositions disclosedherein likely include such digestion action on the carbon from CaNCN.The PAC definition (carbon granules less than 0.15 mm with holes anddramatically enlarged surface areas) describes this lighter particlessuspended in dense fluids effect on CaNCN graphite carbon. The nextsmallest carbon form from graphite may be graphine.

FIG. 14 displays UAN foliar phytotoxicity effects summary results fromof two separate non replicated pansy pots and adjacent sod pads in awater holding tray. The UAN desiccated the pansy and sod pad 100%. Thecarbon containing 5% calcium cyanamide (CaNCN) composition lowered pansyand sod desiccation 65%. The near nil 10× diluted 0.5% CaNCNcomposition, that was QHD resonance treated, lowered the pansy and soddesiccation 35%. Therefore, both the carbon and the QHD resonancecontributed to lowering UAN desiccation.

TABLE 12 2012 CARBON UAN OVER UAN SPRING FERTILIZED FOR BOTH SUMMER CORN& CARBON FALL RYEGRASS/RADISH COVER CROP INFLUENCES Summer Corn 5Bushels Per Acre 3% Winter Cover Crop Ryegrass Root Mass 50% WinterCover Crop Radish Root Mass 88% Winter Cover Crop Ryegrass Top Height117% Winter Cover Crop Radish Top Height 75% Winter Cover Crop RyegrassLeaf Width 100% Winter Cover Crop Radish Leaf Width 67%

FIG. 15 and Table 12 illustrate the influences of carbon feeding soilmicrobes when carbon is in UAN over UAN only. In four field cornreplications at Southern Illinois Arise Research and Discovery Stationthese influences were expressed in magnitudes. Consistent with previousyears studies, the carbon UAN influenced a significant 5 bushels peracre corn yield increase from one spring fertilizer treatment for thesummer corn, which is typically expected to use up its fertilizertreatment. Unexpected, that one treatment further extended itself intothe following second crop of Annual Ryegrass/Tillage Radish winter covercrop. In fact, these latter mixed plant types, pulled at their sameearly stages crop expressed plant responses in much greater magnitudesthan the corn even in early stage. Tillage is reported to damage soilmicrobes. Both these crops were pre-tilled. This indicates that carbonfrom ionized fluid UAN feeds soil microbes to the extent that theythrive under tillage actions to a point of building an increasinglysustainable healthy soil, like from organic farming. Such microbe richsoil holds plant nutrients in the microbes for microbe multiplyinggrowth. Thus, the nutrients are not lost to the environment.

In view of the many possible embodiments to which the principles of thedisclosed invention may be applied, it should be recognized that theillustrated embodiments are only preferred examples of the invention andshould not be taken as limiting the scope of the invention. Rather, thescope of the invention is defined by the following claims. We thereforeclaim as our invention all that comes within the scope and spirit ofthese claims.

1. A fluid composition, comprising: a mixture of about 40 to 20 parts ofdissolved acid or acid-formed approximately neutral pH nitrogen plantnutrient compounds and about 1 to about 5 parts of a mixture ofinsoluble or weakly soluble high pH calcium-formed plant nutrientcompounds, where the dissolved acid comprises nitric acid, phosphoricacid, a weak carbonic acid or a combination thereof and the acid-formednitrogen plant nutrient compounds are in solution and comprise ammoniumnitrate, calcium nitrate, urea ammonium nitrate, calcium ammoniumnitrate, ammonium phosphate, high pH aqueous ammonia or combinationsthereof; and the insoluble or weakly soluble high pH calcium-formedplant nutrient compounds are in solution and comprise calcium cyanamide,gypsum, calcium carbonate, calcium chloride or combinations thereof. 2.The composition of claim 1, where the dissolved acid or acid-formedapproximately neutral pH nitrogen plant nutrient compounds comprisesurea ammonium nitrate (UAN), where the UAN solution comprises about 50%urea nitrogen, 25% ammonia nitrogen and about 25% nitrate nitrogen andthe insoluble or weakly soluble high pH calcium-formed plant nutrientcompounds are in solution comprising H₂O and contain calcium cyanamide.3. The composition of claim 1, where the H₂O present in the fluidmixture comprises less than 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds in the mixture.4. The composition of claim 1, where the H₂O present in the fluidmixture comprises at least 14× the mass of the insoluble or weaklysoluble high pH calcium formed plant nutrient compounds in the mixture.5. The composition of claim 1, where the composition comprises about0.25 percent to about 10 percent by weight calcium cyanamide, such asabout 7 percent to about 8 percent by weight calcium cyanamide. 6.(canceled)
 7. The composition of claim 1, further comprising excreta,such as liquidized manure and/or dairy.
 8. (canceled)
 9. (canceled) 10.The composition of claim 1, where the mixture comprises from about 0.1percent calcium cyanamide to about 25 percent calcium cyanamide, about25 percent to about 50 percent UAN solution and from about 74.99 percentto about 24.99 percent fluid excreta.
 11. The composition of claim 1,where the mixture comprises about 25 percent calcium cyanamide, 25percent to about 50 percent UAN solution and from about 50 percent toabout 25 percent excreta.
 12. The composition of claim 1, furthercomprising at least one non-nitrogen material to the mixture.
 13. Thecomposition of claim 12, where the non-nitrogen material is a plantnutrient, such as phosphorous, potassium, iron, copper, zinc, manganese,magnesium, nickel, boron, magnesium, molybdenum, sulfur, nickel, andmixtures thereof.
 14. (canceled)
 15. The composition of claim 1, furthercomprising an electrolytic suspension agent, such as an aniline ornigrosine or carbon black anionic substances or ionized metal elements,such as silicon, iron, aluminum, carbon or a combination thereof. 16.(canceled)
 17. The composition of claim 1, where the approximatelyneutral pH nitrogen plant nutrient compound mixture comprises a pH ofabout 7.8 and 7.9.
 18. The composition of claim 1, where the fluidcomposition comprises particles of with an about 200 mesh pass through.19. A method of treating excreta, comprising: adding an effective amountof the fluid composition of claim 1 to excreta, where the H₂O present inthe fluid composition comprises at least 14× the mass of the insolubleor weakly soluble high pH calcium formed plant nutrient compounds,thereby forming a mixture and treating excreta.
 20. The method of claim19, where the method is performed in the presence of atmospheric CO₂.21. The method of claim 19, where the excreta is liquidized manureand/or dairy.
 22. (canceled)
 23. The method of claim 19, furthercomprising adding at least one non-nitrogen material to the composition,such as a plant nutrient wherein the plant nutrient is selected from thegroup consisting of phosphorous, potassium, iron, copper, zinc,manganese, magnesium, nickel, boron, magnesium, molybdenum, sulfur,nickel, and mixtures thereof.
 24. (canceled)
 25. (canceled)
 26. Themethod of claim 19, further comprising adding an electrolytic suspensionagent to the composition, where the electrolytic suspension agent isionized aniline or nigrosine or carbon black anionic substances orionized metal elements, such as silicon, iron, aluminum, carbon,magnesium or a combination thereof.
 27. (canceled)
 28. The method ofclaim 19, where the approximately neutral pH nitrogen plant nutrientcompound mixture of claim 1 comprises a pH of about 7.8 and 7.9.
 29. Themethod of claim 19, where the fluid composition comprises particles ofwith an about 60 to about 100 mesh pass through screen size or with anabout 80 to about 100 mesh pass through screen size.
 30. (canceled) 31.The method of claim 19, further comprising applying the fluidcomposition to excreta by spraying.
 32. A method of enhancing plantgrowth, comprising: applying an effective amount of the fluidcomposition of claim 1 in which the H₂O present in the fluid compositioncomprises at least 14× the mass of the insoluble or weakly soluble highpH calcium formed plant nutrient compounds to soil prior to, duringand/or after planting, thereby enhancing plant growth.
 33. The method ofclaim 32, where applying an effective amount comprises applying thecomposition by spraying, soil shank injecting or sprinkler or dripirrigation.
 34. The method of claim 32, where the insoluble or weaklysoluble high pH calcium formed plant nutrient comprises calciumcyanamide.
 35. The method of claim 32, where the fluid compositioncomprises particles of with an about 60 to about 100 mesh pass throughscreen size.
 36. A method of making a fluid composition, comprising:combining a mixture of about 40 to 20 parts of dissolved acid oracid-formed approximately neutral pH nitrogen plant nutrient compoundsto about 1 to about 5 parts of a mixture of insoluble or weakly solublehigh pH calcium-formed plant nutrient compounds, where the dissolvedacid comprises nitric acid, phosphoric acid, a weak carbonic acid or acombination thereof and the acid-formed nitrogen plant nutrientcompounds are in solution and comprise ammonium nitrate, calciumnitrate, urea ammonium nitrate, calcium ammonium nitrate, ammoniumphosphate, high pH aqueous ammonia or combinations thereof; and theinsoluble or weakly soluble high pH calcium-formed plant nutrients arein solution and comprise calcium cyanamide, gypsum, calcium carbonate,calcium chloride or combinations thereof, thereby forming a fluidcomposition. 37-51. (canceled)
 52. A method of digesting insoluble orweakly soluble high pH calcium-formed plant nutrient compounds to formionized calcium compounds, comprising: combining a mixture of about 40to about 20 parts of dissolved acid or acid-formed approximately neutralpH nitrogen plant nutrient compounds to about 1 to about 5 parts of amixture of insoluble or weakly soluble high pH calcium-formed plantnutrient compounds, where the dissolved acid comprising nitric acid,phosphoric acid, a weak carbonic acid or a combination thereof and theacid-formed nitrogen plant nutrient compound are in solution andcomprise ammonium nitrate, calcium nitrate, urea ammonium nitrate,calcium ammonium nitrate, ammonium phosphate, high pH aqueous ammonia orcombinations thereof and hydrolyze the insoluble or weakly soluble highpH calcium-formed plant nutrient compounds in solution which comprisecalcium cyanamide, gypsum, calcium carbonate, calcium chloride orcombinations thereof, thereby forming ionized calcium compounds andinsoluble carbon.
 53. (canceled)
 54. (canceled)
 55. A composition ofclaim 1, where the composition becomes or is hot in which thecomposition is about 60° F. to about 300° F. or about 0° F. to about 80°F.
 56. (canceled)
 57. (canceled)